WO2008038504A1 - Particule de résine expansible, particule expansée, objet mousse et procédé destiné à les produire - Google Patents

Particule de résine expansible, particule expansée, objet mousse et procédé destiné à les produire Download PDF

Info

Publication number
WO2008038504A1
WO2008038504A1 PCT/JP2007/067441 JP2007067441W WO2008038504A1 WO 2008038504 A1 WO2008038504 A1 WO 2008038504A1 JP 2007067441 W JP2007067441 W JP 2007067441W WO 2008038504 A1 WO2008038504 A1 WO 2008038504A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
thermoplastic resin
weight
rubber component
resin particles
Prior art date
Application number
PCT/JP2007/067441
Other languages
English (en)
Japanese (ja)
Inventor
Shotaro Maruhashi
Hidekazu Oohara
Original Assignee
Kaneka Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kaneka Corporation filed Critical Kaneka Corporation
Priority to JP2008536319A priority Critical patent/JPWO2008038504A1/ja
Publication of WO2008038504A1 publication Critical patent/WO2008038504A1/fr

Links

Classifications

    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/04—Polymers provided for in subclasses C08C or C08F
    • 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
    • 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
    • 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
    • C08J2325/08—Copolymers of styrene
    • C08J2325/12—Copolymers of styrene with unsaturated nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L21/00—Compositions of unspecified rubbers

Definitions

  • Foamable resin particles, foamed particles, foam and production method thereof are foamable resin particles, foamed particles, foam and production method thereof.
  • the present invention is compatible with plastic lightening members, automotive members, architectural heat insulating members, repeated drops, high cushioning packaging materials, etc., and has both crack resistance, high resistance, and compressive strength.
  • the present invention relates to a foam, and thermoplastic resin particles, expanded particles, expandable resin particles which are raw materials thereof, and methods for producing them.
  • Polystyrene foams obtained by foam-molding expandable polystyrene resin particles in which polystyrene resin particles are impregnated with a foaming agent are inexpensive and widely used among general-purpose thermoplastic resin foams. It is well known that it is more fragile than other foams.
  • Patent Documents 10 to 12 an impregnation polymerization method in which a particulate styrene polymer is impregnated with a conjugation monomer or the like
  • Patent Documents 13 to; 15 a method using a polyethylene polystyrene copolymer
  • Patent Documents 13 to; 15 a method using a polyethylene polystyrene copolymer
  • Patent Documents 13 to; 15 graft polymerized with acrylate monomer on butadiene rubber, and then graft polymerized styrene monomer and cyanide bur compound to acrylonitrile styrene resin.
  • Dispersed using an extruder or the like! / A method using a so-called AAS resin (Patent Document 16) is used.
  • the foams obtained by these methods have improved crack resistance than polystyrene-based foams, but as a result of introducing a softer component than polystyrene, the foams obtained by these methods The compressive strength tended to be smaller than that of polystyrene foam.
  • Patent Document 20 a method of applying rubber-like latex to expandable polystyrene resin particles or the like
  • softening foam particles There is a method for applying resin emulsion (Patent Document 21).
  • Patent Document 1 Japanese Patent Publication No. 47-18428
  • Patent Document 2 JP-A-7-90105
  • Patent Document 3 Japanese Patent Laid-Open No. 11 279368
  • Patent Document 4 JP-A-11 228720
  • Patent Document 5 Japanese Patent Laid-Open No. 11 147970
  • Patent Document 6 Japanese Patent Laid-Open No. 11 21367
  • Patent Document 7 JP-A-8 188669
  • Patent Document 8 Japanese Patent Laid-Open No. 7-11043
  • Patent Document 9 Japanese Patent Laid-Open No. 7-188452
  • Patent Document 10 JP-A-6-49263
  • Patent Document 11 W ⁇ 98 / 29485 pamphlet
  • Patent Document 12 WO2001 / 048068 Nonfret
  • Patent Document 13 JP-A-8-059754
  • Patent Document 14 Japanese Patent Publication No. 58-051010
  • Patent Document 15 Japanese Patent Laid-Open No. 62-280237
  • Patent Document 16 Japanese Unexamined Patent Publication No. 2001-247709
  • Patent Document 17 Japanese Patent Publication No. 58-42210
  • Patent Document 18 Japanese Patent Publication No.59-7729
  • Patent Document 19 Japanese Patent Publication No. 63-24538
  • Patent Document 20 JP 2005-220174 A
  • Patent Document 21 Japanese Unexamined Patent Application Publication No. 2005-264121
  • the present invention is suitable for plastic weight-reducing members, automotive members, heat insulating members for construction, repeated drop! /, Shock-absorbing packaging materials, etc.
  • the thermoplastic resin particles, the foam particles, and the foam resin particles that are raw materials thereof, and the production methods thereof.
  • the present inventors have a concentric layer structure in a cross section passing through the center of the expandable thermoplastic resin particles, and at least one layer is a layer containing 10% by weight or more of a rubber component. It was found that the expandable thermoplastic resin particles satisfy both high cracking resistance and high compressive strength when formed into a foamed molded product, and the present invention was completed.
  • the first aspect of the present invention is a foaming foam having a concentric layer structure in a cross section passing through the center of the expandable thermoplastic resin particles, wherein at least one layer is a layer containing 10% by weight or more of a rubber component. Relates to a thermoplastic resin particle.
  • the foamable thermoplastic resin particles are preferred! /
  • Expandable thermoplastic resin particles having at least one layer containing less than 10% by weight of a rubber component outside the layer containing 10% by weight or more of the rubber component,
  • the layer structure is a three-layer structure of a central layer, an intermediate layer, and an outer layer
  • the intermediate layer is a layer that contains 10% by weight or more of the rubber component
  • the central layer and the outer layer are layers that contain less than 10% by weight of the rubber component.
  • Expandable thermoplastic resin particles having a glass transition temperature of the rubber component of 20 ° C or lower
  • expandable thermoplastic resin particles described above is expanded particles obtained by expanding the expandable thermoplastic resin particles described above, and as another preferred LV ⁇ embodiment, A foamed product obtained by in-mold molding the described foamed particles.
  • the second aspect of the present invention relates to expanded particles having a layer containing 10% by weight or more of a rubber component in the surface cell membrane of the expanded particles.
  • foam particles are preferred! /
  • the surface cell membrane of the expanded particles has a layer structure, and the layer structure is a three-layer structure of an inner layer, an intermediate layer, and an outer layer, and the intermediate layer is a layer containing 10% by weight or more of a rubber component. Expanded particles whose center layer and outer layer are layers containing less than 10% by weight of a rubber component,
  • another preferred embodiment related to the above-mentioned expanded particles is a foam obtained by molding the above-mentioned expanded particles in a mold.
  • a third aspect of the present invention is that a monomer composition containing a macromonomer is water-based polymerized, has a concentric layer structure in a cross section passing through the center of the thermoplastic resin particles, and at least one layer is a rubber component.
  • the macromonomer has at least two polymerizable terminal groups each having at least one polymerizable reactive group.
  • the present invention relates to a method for producing thermoplastic resin particles having the layer structure described above.
  • a fourth aspect of the present invention is the process through the center of the thermoplastic resin particles obtained by the production method described above.
  • the present invention relates to a thermoplastic resin particle having a layer structure having a concentric layer structure in a cross section, wherein at least one layer is a layer containing 10% by weight or more of a rubber component.
  • a fifth aspect of the present invention relates to expandable thermoplastic resin particles having a layer structure in which the thermoplastic resin particles described above contain a foaming agent.
  • a sixth aspect of the present invention relates to a foamed particle obtained by foaming the foamable thermoplastic resin particles described above.
  • a seventh aspect of the present invention relates to a foam obtained by in-mold molding of the foamed particles described above.
  • a foam having both high crack resistance and high compressive strength can be suitably used as a plastic weight-reducing member, a member for automobiles, a heat insulating member for construction, and a shock-absorbing packaging material with many repeated drops.
  • FIG. 1 is a schematic diagram for explaining a layer structure of particles having a layer structure which is a thermoplastic resin particle or an expandable thermoplastic resin particle of the present invention, and FIG. 1 (a) is a thermoplastic resin.
  • FIG. 1 is a perspective view of a cross-section obtained by cutting the particle or foamed thermoplastic resin particle into a half in a plane passing through the center, and FIG. It is.
  • FIG. 2 is a diagram showing a cross-section of expanded particles obtained by expanding general expandable styrene resin particles
  • FIG. 2 (a) is a scanning electron micrograph thereof
  • FIG. 2 (b) is a part thereof
  • Fig. 2 (c) is a schematic drawing conceptually depicting the part corresponding to Fig. 2 (b).
  • FIG. 3 Transmission electron micrograph of the surface of the cross section of the expandable thermoplastic resin particle of the present invention.
  • FIG. 4 is a transmission electron micrograph further enlarging the vicinity of the surface of FIG.
  • FIG. 5 is a transmission electron micrograph of a cross section of the expanded particle of the present invention.
  • the expandable thermoplastic resin particles of the present invention have a concentric layer structure at the cross-section passing through the center of the expandable thermoplastic resin particles, and at least one layer is a layer containing 10% by weight or more of a rubber component (hereinafter referred to as “the rubber component”). Simply referred to as “rubber layer”).
  • the rubber component a rubber component
  • a preferable range of the rubber component amount in the rubber layer is 15% by weight or more, and a more preferable range is 20% by weight or more. The more rubber components, the easier it is to improve crack resistance.
  • the upper limit of the amount of the rubber component in the rubber layer is not particularly limited, but 98% or less is preferable and 90% or less is more preferable 75% in order to make the rubber in the rubber layer easily have a microphase separation structure. % Or less is particularly preferable.
  • the concentric layer structure referred to in the present invention means that a cross section passing through the center of the expandable thermoplastic resin particles has a structure as shown in FIG. Note that although spherical particles are shown in FIG. 1, they may be elliptical rotating bodies, cylindrical shapes, and the like.
  • the center of the expandable thermoplastic resin particles usually corresponds to the center of gravity of the expandable thermoplastic resin particles. The same applies to the layer structure of thermoplastic resin particles having a concentric layer structure in the present invention before the foaming agent is impregnated.
  • the foamable thermoplastic resin particles shown in FIG. 1 have a three-layer structure. That is, in the case of the foamable thermoplastic resin particles in FIG. 1, the intermediate layer 2 as the second layer exists between the inner layer 3 as the third layer and the outer layer 1 as the first layer, and these three layers. Are formed concentrically.
  • Such a layer structure is obtained by observing the cross section of the expandable thermoplastic resin particles with an optical microscope or by collecting an ultrathin section from the cross section of the expandable thermoplastic resin particles and observing with a transmission electron microscope. It can be confirmed by the method to do.
  • a transmission electron microscope it is possible to use the RuO staining method and OsO staining method depending on the type of resin component.
  • the rubber component of the present invention refers to a resin component having a glass transition temperature lower than room temperature.
  • the resin component having a glass transition temperature lower than room temperature is a layer. This refers to the state of 10% or more by weight.
  • the rubber component of the present invention preferably has a glass transition temperature of 120 ° C or lower, more preferably 40 ° C or lower. When the glass transition temperature is within this range, the effect of improving crack resistance is particularly high. Note that the glass transition temperature of the rubber component, the glass transition temperature of the rubber component in the case of the rubber component 100 parts by weight 0/0.
  • a conventional method can be used. For example, a method of analyzing the composition of concentric layers by microinfrared spectroscopy (IR) or the like can be used.
  • IR microinfrared spectroscopy
  • a method of specifying a component by NMR or other methods and then specifying a component amount of the layer by microinfrared spectroscopy can be used.
  • the expandable thermoplastic resin particles having a layer structure including a rubber layer are obtained by foaming the expandable thermoplastic resin particles into foamed particles, and further molding the foamed particles in a mold to obtain a foamed product.
  • high crack resistance can be imparted.
  • the rubber component when the rubber component is introduced into the normal foamable thermoplastic resin particles, it is not a rubber component, and when the rubber component is introduced into the base resin component made of resin, the rubber component is introduced! /, NA! /, The compressive strength when foamed tends to be lower than in the case of the base resin component, but by adopting a concentric rubber layer form, the compressive strength is reduced. No or very slight decline.
  • the expandable thermoplastic resin particles having a layer structure including a rubber layer can provide a foam having both high crack resistance and high compressive strength.
  • the thickness of the rubber layer is not particularly limited, but foam is used to produce a foam at a lower cost.
  • the rubber layer thickness is preferably 10% or less of the particle diameter of the expandable thermoplastic resin particles, more preferably 7% or less. Particularly preferably, it is 5% or less. From the viewpoint of crack resistance, the rubber layer thickness is preferably 0.5% or more, more preferably 1.0% or more, and particularly preferably 1.5% or more of the particle diameter of the expandable thermoplastic resin particles. is there.
  • the rubber content of the entire expandable thermoplastic resin particles is not particularly limited! /, But in order to produce a foam at a lower cost, a pre-foaming machine and a molding machine normally used with expanded styrene are used. In some cases, it is preferably 30% by weight or less, more preferably 20% by weight or less, and particularly preferably 15% by weight or less. Further, the rubber content is preferably 1% by weight or more from the viewpoint of crack resistance, more preferably 2% by weight or more, and particularly preferably 4% by weight or more.
  • the rubber layer does not affect the crack resistance! /, And the cross-section of the concentric layer structure is acceptable even if there is a defect (such as a missing part of the rubber layer) as long as it is about If the defect part is less than 50% in terms of area.
  • the defective portion is preferably less than 30%, more preferably less than 20%, and particularly preferably less than 10%.
  • foaming heat which does not have a rubber layer within the range not departing from the gist of the present invention or which may contain foaming thermoplastic resin particles having a defective portion of 50% or more is mixed.
  • the mixing ratio of the plastic resin particles is preferably 20% by weight or less, more preferably 10% by weight or less, and particularly preferably 5% by weight or less.
  • non-rubber layer In the expandable thermoplastic resin particles of the present invention, at least one layer containing less than 10% by weight of a rubber component (hereinafter sometimes simply referred to as "non-rubber layer") exists outside the rubber layer. It is preferable to do.
  • the non-rubber layer may be a layer made of a resin component containing no rubber component.
  • the expandable thermoplastic resin particle of the present invention has a surface that passes through the center of the expandable thermoplastic resin particle and has a surface of the expandable thermoplastic resin particle and a depth of 10% of the diameter in the diameter direction from the surface. It is more preferable to have a layer containing 10% by weight or more of the rubber component therebetween.
  • the expandable thermoplastic resin particles of the present invention preferably have a three-layer structure including a central layer, an intermediate layer, and an outer layer, and the intermediate layer is a layer containing 10% by weight or more of a rubber component.
  • an intermediate layer 2 as a second layer is concentrically formed between a central layer 3 as a third layer and an outer layer 1 as a first layer.
  • the center layer and the outer layer is preferably a layer der Rukoto containing less than 10 weight 0/0 a rubber component.
  • the layer containing 10% by weight or more of the rubber component has a micro phase separation structure.
  • Microphase separation structure means that two or more kinds of polymers are phase-separated in a mixture containing two or more kinds of high molecules, and the size of this phase is about several to several tens of nanometers. Say that it is in a state.
  • peeling from the layer containing less than 10% by weight of the rubber component is unlikely to occur.
  • the foamable thermoplastic resin particles as described above are preferably obtained by impregnating a foaming agent into a thermoplastic resin obtained by polymerizing a monomer composition containing a macromonomer.
  • a method for producing a thermoplastic resin particle having a layer structure by polymerizing a monomer composition containing a macromonomer is a method of producing a thermoplastic resin particle having a layer structure by a general multi-stage polymerization method. There is a tendency to simplify manufacturing equipment that is much more efficient than the manufacturing method.
  • thermoplastic resin particles having a layer structure using a monomer composition containing a macromonomer, as described later, a macromonomer and a base resin component that becomes a resin component other than a rubber component
  • a radical-reactive monomer other than the macromonomer such as a bull-type monomer
  • thermoplastic resin particles having a layer structure can be produced.
  • too much macromonomer If the amount is too small or too large, it is difficult to form a layer structure. Therefore, it is preferable to adjust the amount of the macromonomer used according to the target layer structure.
  • thermoplastic resin obtained by polymerizing a monomer composition containing a macromonomer, which is a rubber component, with a foaming agent is preferable as a production method for introducing a rubber component.
  • the macromonomer in the present invention is a high molecular weight monomer having a polymerizable reactive group at the end of the polymer, and the number average molecular weight is not particularly limited, but is preferably in the range of 1000 or more and 200000 or less. More preferably, it is 100000 or less, and most preferably 40000 or less. If the molecular weight force is greater than 00000, the viscosity of the macromonomer will increase and handling will be difficult # 1.
  • a resin component other than the rubber component is referred to as a base resin component. It is preferable that the base resin component used in the present invention is not limited! / Is a polystyrene resin! /!
  • polystyrene resins include those obtained by polymerizing styrene monomers such as styrene derivatives such as styrene, ⁇ -methyl styrene, paramethyl styrene, t-butyl styrene and chlorostyrene. These monomers can be used alone or in combination of two or more. Of these, styrene is particularly preferred.
  • Various monomers such as amide group-containing bulle monomers such as acrylamide and methacrylamide may be copolymerized without departing from the spirit of the present invention.
  • a phthalonitrile-styrene copolymer resin obtained by copolymerizing a styrene monomer and a cyanide bur monomer is more preferable.
  • the amount of styrene in the base resin component is preferably 40% by weight or more, more preferably 50% by weight or more, and particularly preferably 65% by weight or more.
  • examples of the acrylonitrile-styrene copolymer resin include styrene monomers such as styrene, styrene derivatives such as styrene, ⁇ -methylstyrene, paramethylstyrene, t-butylstyrene, chlorostyrene, and acrylonitrile.
  • Shear such as metathalonitrile
  • the amount of styrene is preferably 40% by weight or more, more preferably 50% by weight or more, particularly preferably 65% by weight or more, and usually 95% by weight or less. 92% by weight or less is more preferred and 90% by weight or less is particularly preferred.
  • acrylic acid monomers methacrylic acid monomers, maleic anhydride, maleic acid, monoalkyl esters and dialkyl esters of maleic acid, monoalkyl esters and dialkyl esters of fumaric acid and fumaric acid
  • Various monomers such as maleimide monomers, amide group-containing butyl monomers such as acrylamide and methacrylamide may be copolymerized within the scope of the present invention.
  • the expandable thermoplastic resin particles of the present invention preferably have a particle size of 0.3 to 3 mm.
  • the particle diameter of the thermoplastic resin particles before containing the foaming agent of the present invention is preferably in the same range as above.
  • the rubber component used in the present invention is not particularly limited. Isoprene-based rubber, butadiene-based rubber, styrene-butadiene-based rubber, black-opened-prene rubber, nitrile-based rubber, petitnole rubber, ethylene-propylene rubber, Urethane rubber, silicone rubber, acrylic rubber, fluororubber, etc. can be exemplified, and these rubber components can be used alone or in combination. Among these, it is more preferable to use a rubber made of an acrylate-based polymer, and it is particularly preferable to use a rubber formed from an ethyl acrylate-based polymer or a rubber formed from a butyl acrylate-based polymer. Masle.
  • the polymerizable reactive group present at the molecular end of the macromonomer is not particularly limited, and examples thereof include an aryl group, a butyl silyl group, a butyl ether group, and a dicyclopentagenyl group. From the copolymerization reactivity with other monomers It is preferable that at least one is a carbon-carbon double bond.
  • R is hydrogen or an organic group having 1 to 20 carbon atoms, and H -CH -CH CH-(CH) CH (n is an integer of 2 to 19 inclusive.
  • the group selected from C H -CH OH CN is preferred, more preferably one H
  • the method for producing the polymer that is the main chain of the macromonomer used in the present invention is not particularly limited, but is preferably produced by radical polymerization!
  • the monomer constituting the polymer main chain of the macromonomer various kinds of monomers that are not particularly restricted can be used.
  • Acrylic acid ester monomers are preferred, for example, alkyl alkyl ester monomers having 1 to 10 carbon atoms in the alkyl group such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and the like can be preferably used. Particularly preferred is butyl acrylate.
  • the above monomer may be copolymerized with a monomer other than those described above. In that case, it is preferable that the above monomer is contained in an amount of 40% by weight or more.
  • the content of the macromonomer contained in the monomer composition should be 30% by weight or less. 20% by weight or less is more preferable, and 10% by weight or less is particularly preferable.
  • the lower limit of the macromonomer content is preferably 1% by weight or more, more preferably 2% by weight or more, and particularly preferably 3% by weight or more.
  • the expanded particle of the present invention is an expanded particle having a layer containing 10% by weight or more of a rubber component in the surface cell membrane of the expanded particle.
  • FIG. 2 shows a scanning electron micrograph of a cross section of expanded particles obtained by expanding general expandable polystyrene resin particles.
  • the cell structure shown in Fig. 2 is obtained.
  • a portion called the surface cell film is located in the outermost layer of the expanded particles.
  • Figure 2 (a) shows expandable styrene resin
  • FIG. 2 is a scanning electron micrograph of a cross-section of expanded particles obtained by foaming particles.
  • FIG. 2 (b) is an enlarged scanning electron micrograph of a portion surrounded by a rectangular frame in FIG. ) Is a schematic diagram conceptually depicting the portion corresponding to FIG. 2 (b).
  • a portion called the surface cell membrane is located in the outermost layer of the expanded particles indicated by reference numeral 4 in the schematic diagram of FIG. 2 (c).
  • the surface cell membrane of the expanded particles has a layer containing 10% by weight or more of the rubber component, it exists in the cross section of the expanded body when molded in the mold, compared with the case of having the layer inside the expanded particles.
  • the existence probability of the layer structure increases.
  • the foamed particles of the present invention preferably have a layer containing 10% by weight or more of the rubber component in the surface cell membrane 4 of the foamed particles.
  • the surface cell film 4 itself has a layer structure, and the layer structure has a three-layer structure of an inner layer, an intermediate layer, and an outer layer, and the intermediate layer contains a rubber component. It is a layer containing 10% by weight or more, and the inner layer and the outer layer are preferably layers containing less than 10% by weight of the rubber component.
  • the glass transition temperature of the rubber component used is preferably 20 ° C or lower, more preferably 40 ° C or lower. Rubber components with a glass transition temperature of 120 ° C or less tend to have a particularly high effect of improving crack resistance.
  • the present invention is preferably foamed particles obtained by foaming foamable thermoplastic resin particles obtained by polymerizing a monomer composition containing a macromonomer.
  • the method for producing expandable thermoplastic resin particles having a layer structure by polymerizing a monomer composition containing a macromonomer is to produce expandable thermoplastic resin particles having a layer structure by a general multi-stage polymerization method. Manufacturing facilities that are much more efficient than the method tend to be simplified.
  • the expanded particles of the present invention preferably have a particle size of 0.3 to 10 mm. More preferably, it is 0.5 to 8 mm, and particularly preferably 0.7 to 7 mm.
  • the particle diameter is smaller than 0.3 mm, the fusion of the foamed particles during molding in the mold tends to be poor.
  • it is larger than 10 mm the filling property tends to be deteriorated when molding in the mold as expanded particles.
  • the present invention relates to a heat having a layer structure in which a monomer composition containing a macromonomer is water-based polymerized.
  • the manufacturing method of a plastic resin particle is included.
  • a method for producing thermoplastic resin particles having a layer structure a method of polymerizing in multiple stages in emulsion polymerization has been common.
  • the present inventors have found a method of easily producing thermoplastic resin particles having a layer structure by subjecting a monomer composition containing a macromonomer to aqueous polymerization.
  • the method for producing thermoplastic resin particles of the present invention includes a macromonomer having a radical reactive functional group and a radical reactive monomer other than the macromonomer (hereinafter referred to as a radical reactive monomer other than a macromonomer, It is preferable to carry out aqueous polymerization of a monomer composition comprising “abbreviated as“ radical reactive monomer ””. When a radical-reactive monomer composition is used, reaction control of aqueous polymerization is facilitated.
  • the aqueous polymerization is preferably suspension polymerization, emulsion polymerization, soap-free polymerization, or dispersion polymerization.
  • suspension polymerization is particularly preferred.
  • existing polymerization equipment can be used, and suspension polymerization is the most preferable production method for producing a preferred average particle size as the expandable resin particles.
  • the macromonomer used in the production method of the present invention preferably has at least one polymerizable reactive group at each of at least two molecular ends.
  • a macromonomer having at least one polymerizable reactive group at each of two molecular ends tends to facilitate the formation of a layer structure.
  • the types and use ratios of the monomers (radical reactive monomers other than the macromonomer, such as bull monomers) for constituting the base resin component other than the rubber component used together with the macromonomer are as described above.
  • the monomer composition is polymerized as described above to obtain a thermoplastic resin.
  • the polymerization method is not particularly limited, but the polymerization is particularly preferably carried out by a polymerization method selected from suspension polymerization or fine suspension polymerization as described above.
  • Examples of the suspension stabilizer used in the present invention include water-soluble polymers such as polybulal alcohol, methylcellulose, polyvinylenopyrrolidone, and polyacrylamide, magnesium pyrophosphate, calcium phosphate, hydroxyapatite, and the like.
  • a sparingly soluble inorganic salt or the like can be used, and a surfactant may be used in combination.
  • anionic surfactants such as sodium oleoyl sulfonate and sodium dodecylbenzene sulfonate are used. It is preferable to use a sex agent together!
  • the particle size of the thermoplastic resin particles and the expandable thermoplastic resin particles can be adjusted by the amount of the suspension stabilizer used.
  • a radical-generating polymerization initiator generally used in the production of a thermoplastic polymer can be used.
  • Typical examples include, for example, benzoyl peroxide, lauroyl peroxide, t-butyl perbenzoate, t-butyl perpivalate, t-butylinoperoxyisopropinolecarbonate, tert-butylenoperoxy Acetate, 2,2-di-t-butylperoxybutane, di-t-butylperoxyhydroterephthalate, 1,1-di (t-butylperoxy) 3,3,5-trimethylolcyclohexane, 1,1-di (T-butylperoxy) cyclohexane, 1,1-di (t-amylperoxy) 3,3,5-trimethylcyclohexane, 1,1-di- (t- (t-amylperoxy) 3,3,5-trimethylcyclohexane, 1,1-di-
  • the polymerization of the monomer composition in the present invention is generally used for polymerization of mercaptan-based chain transfer agents such as n-octylmer power ptane, n-dodecyl mercaptan, t-decyl mercaptan and acrylonitrile-styrene resin.
  • mercaptan-based chain transfer agents such as n-octylmer power ptane, n-dodecyl mercaptan, t-decyl mercaptan and acrylonitrile-styrene resin.
  • the ⁇ -methyl styrene dimer used may be used as a polymerization regulator. Use of a-methylstyrene dimer is preferred because it reduces the odor of the foam!
  • a plasticizer may be added to the foamable thermoplastic resin of the present invention in order to adjust foamability and the like.
  • Conventional plasticizers can be used, but if it is necessary to reduce the emission of volatile organic components from the foam, it is better to use a plasticizer with a high boiling point or a plasticizer that does not have a boiling point at room temperature. .
  • fatty acid esters such as dioctyl phthalate, di-2-ethylhexyl phthalate, dibutyl phthalate, and butyl benzyl phthalate, phthalate esters, dibutyl sebacate, dioctyl adipate, diisobutyl adipate, and palm oil
  • Glycerin fatty acid esters such as palm kernel oil, palm oil, rapeseed oil, rapeseed hardened fractionated oil, and hardened soybean oil. These may be used alone or in combination of two or more.
  • additives that are generally used in the production of expandable polystyrene resin particles such as flame retardants, ultraviolet absorbers, antistatic agents, conductive agents, and particle size distribution modifiers, are appropriately added. That's the power S.
  • a macromonomer, a styrene monomer, and a cyanide bulle monomer are used as a polymerization initiator and other additives.
  • examples thereof include a method in which a polymerization reaction is started after being dispersed in an aqueous medium in the presence and a foaming agent is added during the polymerization, or a method of impregnating the foaming agent after the polymerization.
  • thermoplastic resin particles obtained as described above by impregnating the thermoplastic resin particles obtained as described above with a foaming agent, expandable thermoplastic resin particles having a layer structure can be obtained.
  • foaming agent foamable thermoplastic resin particles can be obtained by a known method, for example, by adding a foaming agent during suspension polymerization or after polymerization.
  • blowing agent used in the present invention examples include generally well-known aliphatic hydrocarbons such as propane, normal butane, isobutane, normal pentane, isopentane and hexane, and fats such as cyclohexane, cyclopentane and cyclobutane.
  • Volatile blowing agents having a boiling point of 80 ° C. or lower such as cyclic hydrocarbons and halogenated hydrocarbons such as trifluoromonochloroethane and difluorodichloromethane, can be used. These may be used alone or in combination of two or more.
  • butane or / and pentane as the foaming agent, with butane being particularly preferred.
  • a foaming agent may be added during the polymerization step, or may be added after the completion of the polymerization step.
  • the foaming agent is usually supplied in an amount such that the foaming agent content of the expandable thermoplastic resin particles is preferably 3 wt% or more and 15 wt% or less. More preferably, it is 4% by weight or more and 10% by weight or less. If it is less than 3% by weight, sufficient foamability cannot be obtained, and if it exceeds 15% by weight, shrinkage and deformation during foam molding tend to increase.
  • the foamable resin particles can be expanded into foamed particles by a method such as using steam in a pre-foaming machine used in the production of expanded polystyrene! /
  • a foam can be obtained by molding the foamed particles in a mold.
  • n-butyl acryloylate at both ends of the acryloyl group was synthesized.
  • the number average molecular weight of the purified macromonomer was 25600, the molecular weight distribution was 1.25, and the glass transition temperature was 54 ° C.
  • the number average molecular weight and the molecular weight distribution were calculated by a standard polystyrene conversion method using gel permeation chromatography (GPC).
  • GPC gel permeation chromatography
  • the glass transition temperature of the macromonomer was measured by DSC.
  • the obtained foamable thermoplastic resin particles were dehydrated in a centrifuge and dried. Average grain When the diameter was measured, it was 0.95 mm.
  • the foamable thermoplastic resin particles were classified to a particle size of 0.84 to 1; 19 mm.
  • the foamed thermoplastic resin particles were pre-foamed to a bulk density of 33.3 kg / m 3 using 0. IMPa water vapor (temperature of about 100 ° C) to obtain pre-foamed particles.
  • pre-expanded particles were cured at room temperature for 1 day, they were filled in a mold cavity of 300 X 600 X 25mm and heated with IMPa water vapor (temperature about 100 ° C) for 20 seconds to obtain a foam. .
  • the test for examining the compressive strength of the foam is performed according to JIS K 7220. Cut a 50 mm x 50 mm x 25 mm specimen from the foam.
  • the thickness of 25 mm is the same as the thickness of the foam molded above. In other words, two surfaces of 50mm x 50mm remain as surface skins, and four surfaces of 50mm x 25mm are surfaces cut out by a vertical slicer.
  • the compression test is performed at a test speed of 10 mm / min so that the surface with the surface skin is up and down.
  • the value A (MPa) of the compressive strength is expressed as the stress when the specimen is compressed 25%.
  • the density C (kg / m 3 ) of the foam was determined by the following formula in accordance with JIS K 6767.
  • G and V were calculated by measuring the weight, vertical, horizontal and height dimensions of the compressive strength test sample. Measuring tools and accuracy are based on JIS K 6767.
  • the falling ball impact test which shows the strength of crack resistance of foam, is conducted in accordance with JIS K 7211-1967. Cut a 200mm x 40mm x 20mm specimen from the foam with a vertical slicer. This specimen has a force S with two 200mm x 40mm surfaces, one of which is the foam skin as it is, and the other is a surface sliced with a vertical slicer. To do.
  • the surface skin of the foam is a portion exposed on the surface of the foam when the foam is molded, and is different from the inside of the foam cut out by the vertical slicer.
  • two 200mm x 20mm surfaces and two 40mm x 20mm surfaces are cut out with a birch cano-less slicer. Prepare 20 specimens.
  • a hard ball of 321 g is dropped with the surface having the surface skin of the test piece as the surface on which the falling ball collides. Calculate the half-height fracture height B (cm) using the formula below. The larger the value! /, The greater the crack resistance.
  • H Test height (cm) when the height level (i) is 0, and the height at which the specimen is expected to break.
  • ⁇ The number of specimens that were destroyed at each level.
  • the required number of test pieces is prepared separately from the 20 test pieces. Using the separately prepared test piece, drop the 321 g hard ball described above onto the test piece. At this time, the test height (the height at which the hard sphere is dropped) is changed at intervals of d (cm), the test is performed, and the minimum height at which the test piece broke is H, and the initial test height is determined as H. Keep it. Next measure Using 20 test specimens to be specified, the falling ball impact test starts from the height, and the nth test piece hits the falling ball impact test!
  • the height interval d (cm) when raising and lowering the test height shall be 5 cm unless inconvenient.
  • the density C (kg / m 3 ) of the foam was determined according to the following formula in accordance with JIS K 6767.
  • FIG. 3 shows the observation results near the surface of the expandable thermoplastic resin particles
  • Fig. 4 shows the observation results obtained by enlarging the surface portion.
  • FIG. 3 shown on the left side of the transmission electron micrograph is a diagram schematically depicting only the outline of the cross section of the expandable thermoplastic resin particle.
  • a photograph of the part of the part surrounded by the square in the figure and corresponding to the vicinity of the surface of the foamed thermoplastic resin particle is observed with a transmission electron microscope, as shown on the right side of FIG. . 5 indicates the surface of the foamable thermoplastic resin particle
  • 6 is the second layer (dense)
  • 7 is the third layer (thin)
  • the second layer of 6 contains 10% by weight or more of the rubber component.
  • the third layer of 7 corresponds to a layer containing less than 10% by weight of rubber component.
  • Fig. 4 shows a transmission electron micrograph further enlarging the area from the reference numeral 6 to the reference numeral 5 in Fig. 3.
  • the thickness of the second layer which was darker than the other parts, was about 22 m.
  • FIG. 5 shows the observation results of the surface cell film of the expanded particles obtained by pre-expanding the expandable thermoplastic resin particles as described above.
  • the surface cell membrane of the expanded particles is a portion indicated by reference numeral 5 in FIG. 2 (c), and FIG. 5 is an observation result of the expanded particles of the embodiment of the present invention in the portion corresponding to reference numeral 5.
  • the foamed particles of the present invention have a three-layer structure in which the surface cell membrane includes an inner layer containing less than 10% by weight of a rubber component, an intermediate layer containing 10% by weight or more of a rubber component, and an outer layer containing less than 10% by weight of a rubber component The thing which consists of is obtained.
  • Acrylonitrile styrene resin (AS resin) with a known blending ratio of acrylonitrile and styrene and butyl acrylate polybutyl acrylate prepared in Production Example 1 are blended in various proportions and dissolved in black mouth form to give a 5 wt% solution. It was.
  • the part (second layer: 6) that is concentrically dyed near the surface of the expandable thermoplastic resin particles in Fig. 3 more deeply than the other part contains 26% by weight of butyl acrylate! . Further, the content of the butyl acrylate component in the third layer (7) portion of FIG. 3 was 3% by weight.
  • Example 2 The same procedure as in Example 1 was carried out except that the amount of styrene charged was 1609. 5 g, and the amount of taro nitrotriol was changed to 505.5 g.
  • Example 2 The same procedure as in Example 1 was conducted except that the amount of styrene charged was 1732/5 g, and the amount of the macromonomer having attalyloyl groups at both ends was 180 g.
  • Example 2 The same procedure as in Example 1 was conducted, except that the amount of styrene charged was 1678 g, the amount of acrylonitrile charged was 527 g, and the amount of macromonomer having an attaylyl group at both ends was 45 g.
  • a molded body was produced in the same manner as in Example 1 except that expandable polystyrene resin particles (product name: “Kanepal NSG”, manufactured by Riki Neka Co., Ltd.) having a resin part of 100% by weight polystyrene were used.
  • expandable polystyrene resin particles product name: “Kanepal NSG”, manufactured by Riki Neka Co., Ltd.
  • Expandable modified styrene resin particles were obtained according to the description in Example 2 of WO2001 / 048068 non-fret (corresponding US Pat. No. 6,770,682B2). Others were carried out in the same manner as in Examples 1 to 4, and molded articles were produced.
  • Molding was carried out in the same manner as in Example 1, except that 2250 g of styrene was charged, 0 g of acrylonitrile was charged, macromonic monomer having an acryloyl group at both ends was Og, and 0.45 g of dibulubenzene was added. The body was made.
  • the amount of styrene charged is 2250g, the amount of acrylonitrile charged is 0g, and both ends are attalyloyl.
  • a molded body was produced in the same manner as in Example 1 except that the amount of the macromonomer having a group was changed to Og and 1.35 g of dibutylbenzene was added.
  • Example 2 The same procedure as in Example 1 was carried out except that the amount of styrene charged was 118.6.6 g, the amount of alitronitrinole charged was 376.4 g, and the amount of macromonomer having both ends of the acryloyl group was 675 g. . Although it was pre-foamed, it was able to foam up to 3.2 times the bulk magnification. Molding was carried out with these pre-expanded particles, but no fusion was observed, and no evaluable foam was obtained.
  • the foam obtained in the present invention has high compressive strength and high crack resistance.
  • the present invention can provide a foam having both high cracking resistance and high compressive strength, it is effective for plastic weight-reducing members, automotive members, thermal insulation members for buildings, and shock-absorbing packaging materials that frequently fall. Available to:

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

L'invention concerne des particules de résine thermoplastique expansibles présentant chacune une structure stratifiée concentrique dans laquelle une partie comprenant le centre de la particule contient un ingrédient caoutchouteux dans une quantité de 10 % en poids ou plus ; des particules expansées obtenues à partir de ces particules ; une mousse ; et un procédé destiné à produire la mousse. La mousse peut combiner une insensibilité élevée à la rupture avec une résistance élevée à la compression et est adaptée pour être utilisée, par exemple, en tant que : élément de réduction du poids dans des plastiques, élément d'automobile, élément d'isolation thermique pour les bâtiments et matériau d'emballage avec rembourrage subissant des chutes répétées.
PCT/JP2007/067441 2006-09-26 2007-09-06 Particule de résine expansible, particule expansée, objet mousse et procédé destiné à les produire WO2008038504A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2008536319A JPWO2008038504A1 (ja) 2006-09-26 2007-09-06 発泡性樹脂粒子、発泡粒子及び発泡体ならびにその製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2006-261106 2006-09-26
JP2006261106 2006-09-26

Publications (1)

Publication Number Publication Date
WO2008038504A1 true WO2008038504A1 (fr) 2008-04-03

Family

ID=39229943

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2007/067441 WO2008038504A1 (fr) 2006-09-26 2007-09-06 Particule de résine expansible, particule expansée, objet mousse et procédé destiné à les produire

Country Status (2)

Country Link
JP (1) JPWO2008038504A1 (fr)
WO (1) WO2008038504A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014193948A (ja) * 2013-03-28 2014-10-09 Sekisui Plastics Co Ltd スチレン系発泡樹脂粒子及びスチレン系発泡成形体
JP2017095532A (ja) * 2015-11-18 2017-06-01 Ｋｊケミカルズ株式会社 発泡性樹脂粒子用ガスバリア剤及びそれを含有する発泡性樹脂粒子
JP2017218575A (ja) * 2016-06-02 2017-12-14 Ｐｓジャパン株式会社 スチレン系共重合体およびその製造方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05202223A (ja) * 1992-01-28 1993-08-10 Idemitsu Petrochem Co Ltd 発泡性スチレン系樹脂粒子
JPH08134252A (ja) * 1994-11-15 1996-05-28 Hitachi Chem Co Ltd 発泡性スチレン系重合体粒子、その製造法及び発泡成形品
JP2005220174A (ja) * 2004-02-03 2005-08-18 Nikka Kaseihin Kk ゴム状ラテックス含有発泡スチレン系樹脂成形品及びその製造方法
JP2005264121A (ja) * 2004-03-22 2005-09-29 Sekisui Plastics Co Ltd ポリスチレン系樹脂発泡粒子およびその製造方法と発泡成形体
JP2006265334A (ja) * 2005-03-23 2006-10-05 Sekisui Plastics Co Ltd 表面改質発泡性ポリスチレン系樹脂粒子とその製造方法、発泡成形体製造用ポリスチレン系樹脂発泡粒子及びポリスチレン系樹脂発泡成形体
WO2006106653A1 (fr) * 2005-03-31 2006-10-12 Kaneka Corporation Cordons de résine thermoplastique extensible et mousse réalisée à partir de ceux-ci

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05202223A (ja) * 1992-01-28 1993-08-10 Idemitsu Petrochem Co Ltd 発泡性スチレン系樹脂粒子
JPH08134252A (ja) * 1994-11-15 1996-05-28 Hitachi Chem Co Ltd 発泡性スチレン系重合体粒子、その製造法及び発泡成形品
JP2005220174A (ja) * 2004-02-03 2005-08-18 Nikka Kaseihin Kk ゴム状ラテックス含有発泡スチレン系樹脂成形品及びその製造方法
JP2005264121A (ja) * 2004-03-22 2005-09-29 Sekisui Plastics Co Ltd ポリスチレン系樹脂発泡粒子およびその製造方法と発泡成形体
JP2006265334A (ja) * 2005-03-23 2006-10-05 Sekisui Plastics Co Ltd 表面改質発泡性ポリスチレン系樹脂粒子とその製造方法、発泡成形体製造用ポリスチレン系樹脂発泡粒子及びポリスチレン系樹脂発泡成形体
WO2006106653A1 (fr) * 2005-03-31 2006-10-12 Kaneka Corporation Cordons de résine thermoplastique extensible et mousse réalisée à partir de ceux-ci

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014193948A (ja) * 2013-03-28 2014-10-09 Sekisui Plastics Co Ltd スチレン系発泡樹脂粒子及びスチレン系発泡成形体
JP2017095532A (ja) * 2015-11-18 2017-06-01 Ｋｊケミカルズ株式会社 発泡性樹脂粒子用ガスバリア剤及びそれを含有する発泡性樹脂粒子
JP2017218575A (ja) * 2016-06-02 2017-12-14 Ｐｓジャパン株式会社 スチレン系共重合体およびその製造方法

Also Published As

Publication number Publication date
JPWO2008038504A1 (ja) 2010-01-28

Similar Documents

Publication Publication Date Title
JP4718597B2 (ja) スチレン改質ポリプロピレン系樹脂粒子、発泡性スチレン改質ポリプロピレン系樹脂粒子、スチレン改質ポリプロピレン系樹脂発泡粒子、スチレン改質ポリプロピレン系樹脂発泡成形体
JP5592558B2 (ja) 複合ポリスチレン系樹脂発泡粒子及びその発泡成形体
JP4056087B2 (ja) 発泡性ポリスチレン系樹脂粒子、その製造法、およびそれを用いた発泡体
JP5553983B2 (ja) スチレン改質ポリエチレン系樹脂粒子および該樹脂粒子より得られる予備発泡粒子
KR101996231B1 (ko) 복합 수지 입자와 그 발포성 입자, 발포 입자 및 발포 성형체
US9127148B2 (en) Modified polystyrene resin particles and manufacturing method therefor, expandable particles and manufacturing method therefor, pre-expanded particles, and expanded molded article
WO2021166947A1 (fr) Mousse hipe et son procédé de production
WO2008038504A1 (fr) Particule de résine expansible, particule expansée, objet mousse et procédé destiné à les produire
JP5324027B2 (ja) スチレン改質熱可塑性ポリウレタン樹脂粒子、発泡性スチレン改質熱可塑性ポリウレタン樹脂粒子、スチレン改質熱可塑性ポリウレタン樹脂発泡粒子、スチレン改質熱可塑性ポリウレタン樹脂発泡成形体及びそれらの製造方法
JP7196078B2 (ja) 発泡性ポリスチレン系樹脂粒子、ポリスチレン系予備発泡粒子及び発泡成形体
JP6855236B2 (ja) 複合樹脂発泡性粒子及びその製法、複合樹脂発泡粒子及びその製法、並びに、複合樹脂発泡成形体及びその製法
JP2014189769A (ja) 改質ポリスチレン系発泡性樹脂粒子とその製造方法及び発泡粒子、発泡成形体
JP2018100380A (ja) ポリスチレン系樹脂発泡性粒子及びその製法、ポリスチレン系樹脂発泡粒子及びその製法、並びに、ポリスチレン系樹脂発泡成形体及びその製法
JP5883703B2 (ja) 緩衝材
JP5296279B2 (ja) 発泡性ポリスチレン系樹脂粒子およびそれを用いた発泡体
JP5739057B2 (ja) 自動車部材
JP2020050790A (ja) スチレン複合ポリエチレン系樹脂発泡粒子、その製造方法及び発泡成形体
WO2014157188A1 (fr) Particules de résine réticulée à base de polystyrène modifié et leur procédé de production, particules expansibles et leur procédé de production, grains pré-expansés, et objet moulé en mousse
JP5914080B2 (ja) 発泡性スチレン系樹脂粒子及びその製造方法
JP6209116B2 (ja) 複合樹脂粒子とその製造方法、発泡性複合樹脂粒子、予備発泡複合樹脂粒子、及び複合樹脂発泡成形体

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 07806882

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2008536319

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 07806882

Country of ref document: EP

Kind code of ref document: A1