WO2022149538A1 - Particules de mousse de résine de polypropylène et article moulé en mousse de résine de polypropylène - Google Patents

Particules de mousse de résine de polypropylène et article moulé en mousse de résine de polypropylène Download PDF

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WO2022149538A1
WO2022149538A1 PCT/JP2021/048735 JP2021048735W WO2022149538A1 WO 2022149538 A1 WO2022149538 A1 WO 2022149538A1 JP 2021048735 W JP2021048735 W JP 2021048735W WO 2022149538 A1 WO2022149538 A1 WO 2022149538A1
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weight
polypropylene
copolymer
foamed particles
particles
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PCT/JP2021/048735
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English (en)
Japanese (ja)
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豊 松宮
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株式会社カネカ
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Priority to CN202180089689.8A priority Critical patent/CN116783240A/zh
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Publication of WO2022149538A1 publication Critical patent/WO2022149538A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/16—Making expandable particles

Definitions

  • the present invention relates to polypropylene-based resin foamed particles and polypropylene-based resin foamed molded article.
  • Polypropylene resin foam molded products are used for various purposes such as automobile interior members, core materials for automobile bumpers, heat insulating materials, cushioning packaging materials, and returnable boxes.
  • the polypropylene-based resin is a crystalline thermoplastic resin
  • the polypropylene-based resin foamed molded product obtained by molding the polypropylene-based resin foamed particles is compared with the non-crystalline thermoplastic resin such as polystyrene after molding. Shrinkage is large. Therefore, in particular, when integrally molding another material such as metal (in the case of insert molding), the metal member may be deformed due to the shrinkage of the polypropylene-based resin foam molded body after molding. That is, in the prior art, it has been difficult to control the dimensions and / or shape of the polypropylene-based resin foam molded product when integrally molding other materials such as metal.
  • Patent Document 1 discloses a technique in which a polypropylene-based resin, an amorphous thermoplastic resin, and a compatibilizer are mixed and used.
  • Patent Document 2 discloses a technique in which a polypropylene-based resin is mixed with a polystyrene-based resin and a polymer mainly composed of a vinyl aromatic compound.
  • an object of the embodiment of the present invention is to provide a polypropylene-based resin foam molded product having (a) almost no shrinkage and deformation after molding, and (b) polypropylene having excellent foamability.
  • the purpose is to provide foamed resin particles.
  • the present inventors have completed the present invention as a result of diligent studies to solve the above-mentioned problems.
  • the polypropylene-based resin foamed particles according to the embodiment of the present invention include 100 parts by weight of the polypropylene-based resin, 5 parts by weight to 60 parts by weight of the polymer containing the acrylonitrile unit and the styrene-based unit, and the hydrogenated styrene-based particles. Includes 3.0 parts by weight to 30.0 parts by weight of the polymer.
  • the method for producing polypropylene-based resin foamed particles includes a foaming step of foaming polypropylene-based resin particles, and the polypropylene-based resin particles are 100 parts by weight of polypropylene-based resin and acrylonitrile. It contains 5 parts by weight to 60 parts by weight of the copolymer including the unit and the styrene-based unit, and 3.0 parts by weight to 30.0 parts by weight of the hydrogenated styrene-based copolymer.
  • FIG. 1 is a schematic view of a foam molded product 100 used for evaluating the amount of deformation.
  • a structural unit derived from an X 1 monomer a structural unit derived from an X 2 monomer, ... And an X n monomer (n is A copolymer containing (an integer of 2 or more) is also referred to as "X 1 / X 2 / ... / X n copolymer".
  • X 1 / X 2 / ... / X n copolymer is not particularly limited in the polymerization mode, and may be a random copolymer or a block copolymer. It may be a graft copolymer or a graft copolymer.
  • X unit the structural unit derived from the X monomer contained in the polymer or the copolymer
  • the polypropylene-based resin foamed particles according to the embodiment of the present invention include 100 parts by weight of a polypropylene-based resin, 5 to 60 parts by weight of a copolymer containing an acrylonitrile unit and a styrene-based unit, and a hydrogenated styrene-based copolymer. Includes 3.0 parts by weight to 30.0 parts by weight.
  • the polypropylene-based resin foamed particles according to the embodiment of the present invention can be molded by a known method to provide a polypropylene-based resin foamed molded product.
  • polypropylene resin foamed particles may be referred to as “foamed particles”
  • polypropylene resin foamed particles according to one embodiment of the present invention may be referred to as “present foamed particles”.
  • the "polypropylene resin foam molded body” may be referred to as a “foam molded body”.
  • the polypropylene-based resin foamed particles according to the embodiment of the present invention have the above-mentioned constitution, it is possible to provide (a) a polypropylene-based resin foamed molded product having almost no shrinkage and deformation after molding, and (b) to be foamable. It has the advantage of being excellent. It can be said that the polypropylene-based resin foamed particles according to the embodiment of the present invention can provide a polypropylene-based resin foamed molded product in which shrinkage and deformation after molding are reduced as compared with the conventional product. In the present specification, reducing the shrinkage of the foamed molded product after molding is also referred to as being excellent in shrinkage.
  • the polypropylene-based resin is intended to be a resin containing 75 mol% or more of structural units derived from a propylene monomer in 100 mol% of all structural units contained in the resin.
  • structural unit derived from propylene monomer may be referred to as "propylene unit”.
  • the polypropylene-based resin may be (a) a homopolymer of propylene, or (b) a block copolymer of propylene and a monomer other than propylene, a random copolymer, or a graft copolymer. It may be well, or (c) a mixture of two or more of these.
  • the polypropylene-based resin may have one or more structural units derived from a monomer other than the propylene monomer in addition to the propylene unit, or may have one or more.
  • the "monomer other than the propylene monomer” used in the production of polypropylene-based resin may be referred to as "comonomer”.
  • the "structural unit derived from a monomer other than the propylene monomer” contained in the polypropylene resin may be referred to as a "comonomer unit".
  • Examples of comonomers include ethylene, 1-butene, isobutene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, 3,4-dimethyl-1-butene, 1-heptene, Examples thereof include ⁇ -olefins having 2 or 4 to 12 carbon atoms such as 3-methyl-1-hexene, 1-octene and 1-decene.
  • polypropylene-based resin examples include polypropylene homopolymers, ethylene / propylene random copolymers, 1-butene / propylene random copolymers, 1-butene / ethylene / propylene random copolymers, and ethylene / propylene block copolymer weights.
  • examples thereof include coalescence, 1-butene / propylene block copolymer, propylene / chlorinated vinyl copolymer, propylene / maleic anhydride copolymer, styrene-modified polypropylene-based resin and the like.
  • the polypropylene-based resin one of these may be used alone, or two or more thereof may be used in combination.
  • the ethylene / propylene random copolymer and the 1-butene / ethylene / propylene random copolymer have good foamability in the obtained foamed particles, and the present molded product has good formability. It is suitable because of its possession.
  • the 1-butene is synonymous with butene-1.
  • Case A the ethylene content in the ethylene / propylene random copolymer or the 1-butene / ethylene / propylene random copolymer is 0.2% by weight to 10.0% by weight in 100% by weight of each copolymer. Is preferable.
  • the ethylene content can also be said to be the content of structural units (ethylene units) derived from ethylene.
  • the content of ethylene units in the ethylene / propylene random copolymer or 1-butene / ethylene / propylene random copolymer is (i) 0.2% by weight or more, the foamed particles in the production of the present foamed particles The foamability and / or the formability of the obtained foamed particles tends to be good, and when (ii) 10.0% by weight or less, the mechanical properties of the foamed molded product obtained from the present foamed particles are deteriorated. There is no fear.
  • the 1-butene content in the 1-butene / ethylene / propylene random copolymer is preferably 0.2% by weight to 10.0% by weight based on 100% by weight of the copolymer.
  • the 1-butene content can also be said to be the content of the constituent units (1-butene units) derived from 1-butene.
  • the content of 1-butene units in the 1-butene / ethylene / propylene random copolymer is (i) 0.2% by weight or more, the foamability of the foamed particles in the production of the present foamed particles and / or The moldability of the obtained foamed particles tends to be good, and when (ii) 10.0% by weight or less, there is no possibility that the mechanical properties of the foamed molded product obtained from the present foamed particles are deteriorated.
  • the total content of the ethylene unit and the 1-butene unit in the 1-butene / ethylene / propylene random copolymer is 0 in 100% by weight of the 1-butene / ethylene / propylene random copolymer. It is preferably 5.5% by weight to 10.0% by weight.
  • the total content of ethylene units and 1-butene units in the 1-butene / ethylene / propylene random copolymer is (i) 0.5% by weight or more, the foamability of the foamed particles in the production of the foamed particles is (i).
  • the melting point of the polypropylene resin is preferably 135.0 ° C to 160.0 ° C, more preferably 138.0 ° C to 158.0 ° C, more preferably 140.0 ° C to 156.0 ° C, and more preferably 143.0 ° C. ⁇ 154.0 ° C. is more preferable, 145.0 ° C. to 152.0 ° C. is further preferable, and 148.0 ° C. to 150.0 ° C. is particularly preferable.
  • the melting point of the polypropylene-based resin is (i) 135.0 ° C. or higher, the foamed molded product obtained from the foamed particles has excellent heat resistance, and when (ii) 160.0 ° C. or lower, the book In the production of foamed particles, it becomes easy to increase the foaming ratio of the foamed particles.
  • the melting point of the polypropylene resin is a value obtained by measuring by the differential scanning calorimetry method (hereinafter referred to as "DSC method").
  • DSC method differential scanning calorimetry method
  • the specific operation procedure is as follows: (1) By raising the temperature of the polypropylene resin 5 mg to 6 mg from 40.0 ° C to 220.0 ° C at a heating rate of 10.0 ° C / min. The polypropylene-based resin is melted; (2) Then, the temperature of the melted polypropylene-based resin is lowered from 220.0 ° C. to 40.0 ° C. at a temperature lowering rate of 10.0 ° C./min to cause the polypropylene-based resin.
  • the temperature of the crystallized polypropylene-based resin is further raised from 40.0 ° C. to 220.0 ° C. at a heating rate of 10 ° C./min.
  • the temperature of the peak (melting peak) of the DSC curve of the polypropylene-based resin obtained at the time of the second temperature rise can be obtained as the melting point of the polypropylene-based resin.
  • the temperature of the peak (melting peak) having the maximum heat of fusion is set to polypropylene. Let it be the melting point of the system resin.
  • the differential scanning calorimeter for example, a DSC6200 type manufactured by Seiko Instruments Co., Ltd. can be used.
  • the melt flow rate (MFR) of the polypropylene resin is not particularly limited, but is preferably 3.0 g / 10 minutes to 30.0 g / 10 minutes, more preferably 4.0 g / 10 minutes to 20.0 g / 10 minutes. , 5.0 g / 10 minutes to 15.0 g / 10 minutes are more preferable, and 6.0 g / 10 minutes to 13.0 g / 10 minutes are particularly preferable.
  • the MFR may be referred to as "melt index (MI)".
  • the MFR of the polypropylene resin When the MFR of the polypropylene resin is 3 g / 10 minutes or more, it tends to be easy to increase the foaming ratio of the foamed particles in the production of the foamed particles.
  • the MFR of the polypropylene resin When the MFR of the polypropylene resin is 30 g / 10 minutes or less, there is no possibility that the bubbles of the obtained foamed particles are communicated with each other, and as a result, (i) the compressive strength of the foamed molded product obtained from the present foamed particles is good. Or (ii) the surface property of the foamed molded product tends to be good.
  • the MFR value of the polypropylene-based resin is a value obtained by measuring under the following conditions using the MFR measuring instrument described in JIS K7210: 1999: Orifice diameter 2.0959 ⁇ . 0.005 mm ⁇ , orifice length 8,000 ⁇ 0.025 mm, load 2.16 kgf, temperature 230 ° C (230 ⁇ 0.2 ° C).
  • Polypropylene resin can be obtained by a known method.
  • the polymerization catalyst for synthesizing the polypropylene-based resin is not particularly limited, and for example, a Ziegler-based catalyst, a metallocene catalyst, or the like can be used.
  • the foamed particles contain 5 to 60 parts by weight of a copolymer containing an acrylonitrile unit and a styrene-based unit with respect to 100 parts by weight of the polypropylene-based resin.
  • the present foamed particles have an advantage that foamed particles having excellent foamability can be obtained, and a foamed molded product having further reduced shrinkage and deformation after molding as compared with the conventional product can be obtained.
  • a copolymer containing an acrylonitrile unit and a styrene-based unit may be referred to as an "AS copolymer".
  • the AS copolymer is an amorphous resin.
  • the AS copolymer is a copolymer containing at least 50 mol% or more of structural units derived from acrylonitrile units or styrene-based units in 100 mol% of all structural units contained in the AS copolymer. Intended for polymers.
  • the AS copolymer is not particularly limited as long as it is a copolymer containing 50 mol% or more of a constituent unit containing at least an acrylonitrile unit and a styrene-based unit, and is, for example, (a) a block copolymer, a random copolymer or a copolymer. It may be a graft copolymer, or (b) a mixture of two or more of these.
  • the styrene-based unit contained in the AS copolymer is a structural unit derived from the styrene-based monomer.
  • examples of the styrene-based monomer include (a) styrene, and (b) ⁇ -methylstyrene, p-methylstyrene, m-methylstyrene, schreib-methylstyrene, 2,4-dimethylstyrene, p-.
  • styrene-based derivatives such as ethyl styrene, m-ethyl styrene, Occasionally-ethyl styrene, t-butyl styrene, and chlorstyrene.
  • styrene-based monomers may be used alone or in combination of two or more. That is, the styrene-based unit contained in the AS copolymer may be one kind or a combination of two or more kinds.
  • the styrene-based unit contained in the AS copolymer preferably contains an ⁇ -methylstyrene unit.
  • the amount of ⁇ -methylstyrene unit in the styrene-based unit contained in the AS polymer is preferably 70% by weight or more, preferably 80% by weight or more, based on 100% by weight of the styrene-based unit contained in the AS polymer. Is more preferable, 90% by weight or more is further preferable, 95% by weight or more is particularly preferable, and 100% by weight is most preferable. That is, the styrene-based unit contained in the AS copolymer is most preferably ⁇ -methylstyrene unit.
  • the amount of the styrene-based unit contained in the AS copolymer (hereinafter, may be referred to as “styrene-based content”) is preferably 20% by weight to 95% by weight in 100% by weight of the AS copolymer. , 50% by weight to 90% by weight, more preferably 55% by weight to 85% by weight, further preferably 60% by weight to 80% by weight, and 65% by weight to 75% by weight. % Is particularly preferable. According to this configuration, there is an advantage that an AS copolymer having good productivity and excellent heat resistance can be obtained.
  • the amount of ⁇ -methylstyrene unit as a styrene-based unit contained in the AS copolymer (hereinafter, may be referred to as “ ⁇ -methylstyrene content”) is 20% by weight in 100% by weight of the AS copolymer. It is preferably ⁇ 95% by weight, more preferably 50% by weight to 90% by weight, further preferably 55% by weight to 85% by weight, still more preferably 60% by weight to 80% by weight. It is more preferably 65% by weight to 75% by weight, and particularly preferably 65% by weight. According to this configuration, there is an advantage that an AS copolymer having good productivity and excellent heat resistance can be obtained.
  • the AS copolymer may have a structural unit other than the acrylonitrile unit and the styrene-based unit (hereinafter, may be referred to as "constituent unit other than AS").
  • the constituent units other than AS include vinyl esters such as vinyl acetate and vinyl propionate; acrylic acid esters such as methyl acrylate and ethyl acrylate; methacrylic esters such as methyl methacrylate and ethyl methacrylate; and ethylene and propylene.
  • the AS copolymer examples thereof include monomers other than the above-mentioned monomers copolymerizable with olefins; maleic anhydride; vinyl chloride; vinylidene chloride; and acrylonitrile units and / or styrene-based units. Since the heat resistance of the AS copolymer is good, the amount of the constituent units other than AS contained in the AS copolymer is preferably 10% by weight or less, preferably 5% by weight or less, based on 100% by weight of the AS copolymer. More preferably, 1% by weight or less is further preferable, and 0% by weight is particularly preferable. That is, it is particularly preferable that the AS copolymer is a copolymer composed of an acrylonitrile unit and a styrene-based unit.
  • AS copolymer examples include acrylonitrile / styrene copolymer, acrylonitrile / ⁇ -methylstyrene copolymer, acrylonitrile / p-methylstyrene copolymer, acrylonitrile / m-methylstyrene copolymer, and acrylonitrile / 4.000.
  • acrylonitrile / ⁇ -methylstyrene copolymer is preferable because it has an advantage that foamed particles having excellent foamability can be obtained. Only one kind of these AS copolymers may be used, or two or more kinds thereof may be used in combination.
  • the glass transition temperature (sometimes referred to as “Tg”) of the AS copolymer is not particularly limited, but is preferably 95 ° C to 140 ° C, more preferably 100 ° C to 135 ° C, and preferably 103 ° C to 130 ° C. More preferably, 105 ° C to 125 ° C is particularly preferable.
  • Tg of the AS copolymer is (i) 95 ° C. or higher, it has an advantage that foamed particles having excellent heat resistance and a foamed molded product can be obtained, and when it is (ii) 140 ° C. or lower, it has an advantage. Effervescent particles with a low open cell ratio can be obtained.
  • the Tg of the AS copolymer is a value obtained by measuring according to JIS-K-7121 using a differential scanning calorimeter [DSC6200 type manufactured by Seiko Instruments Co., Ltd.].
  • the specific operation procedure is as follows (1) to (5): (1) Weigh 5 mg of the AS polymer; (2) In a nitrogen atmosphere, the temperature of the AS polymer is set to 10 The temperature is raised from room temperature to 250 ° C. at ° C./min; (3) the temperature of the heated AS copolymer is lowered from 250 ° C. to room temperature at 10 ° C./min; (4) again of the AS copolymer. The temperature is raised from room temperature to 250 ° C.
  • the MFR of the AS copolymer is not particularly limited, but is preferably 2.0 g / 10 minutes to 15.0 g / 10 minutes, more preferably 3.0 g / 10 minutes to 12.0 g / 10 minutes, and 4.0 g. It is more preferably / 10 minutes to 10.0 g / 10 minutes.
  • the MFR of the AS copolymer is 2.0 g / 10 min to 15.0 g / min, the AS copolymer has excellent compatibility with the polypropylene-based resin, and the obtained resin particles are continuously foamed. Foaming can be reduced. As a result, it has an advantage that foamed particles having a low open cell ratio can be obtained.
  • the MFR value of the AS copolymer is a value obtained by measuring under the following conditions using the MFR measuring instrument described in JIS K7210: 1999: Orifice diameter 2.0959. ⁇ 0.005 mm ⁇ , orifice length 8,000 ⁇ 0.025 mm, load 2.16 kgf, temperature 230 ° C (230 ⁇ 0.2 ° C).
  • the content of the AS copolymer in the foamed particles is 5 parts by weight to 60 parts by weight, more preferably 5 parts by weight to 50 parts by weight, and 8 parts by weight to 50 parts by weight with respect to 100 parts by weight of the polypropylene-based resin. Parts by weight are more preferable, parts by weight 10 to 40 parts by weight are more preferable, parts by weight 13 to 40 parts by weight are more preferable, parts by weight 15 to 35 parts by weight are further preferable, and parts by weight 20 to 30 parts by weight are particularly preferable.
  • the content of the AS copolymer is (a) 5 parts by weight or more with respect to 100 parts by weight of the polypropylene resin, foamed particles having excellent foamability can be obtained, and after molding as compared with the conventional product.
  • the polypropylene-based resin foamed particles according to the embodiment of the present invention contain 3.0 parts by weight to 30.0 parts by weight of the hydrogenated styrene-based copolymer.
  • the hydrogenated styrene-based copolymer has a compatibilizing effect between the polypropylene-based resin and the AS copolymer. In other words, the hydrogenated styrene-based copolymer can function as a compatibilizer.
  • the foamed particles can be foamed with excellent foamability, and the shrinkage and deformation after molding are further reduced as compared with the conventional product. It has the advantage that a molded product can be obtained.
  • the "hydrogenated styrene-based copolymer” is a block copolymer containing a styrene block composed of only styrene units and a conjugated diene-based block composed of only conjugated diene-based units (hereinafter, copolymer weight). It is a copolymer obtained by hydrogenating (also referred to as coalescence X). In the present specification, “hydrogenation” may be referred to as "hydrogenation”.
  • the "hydrogenated styrene-based copolymer” refers to the copolymer X so that at least a part of the carbon-carbon double bond in the conjugated diene-based unit of the copolymer X is saturated. Intended is a copolymer obtained by hydrogenation.
  • the conjugated diene-based unit contained in the copolymer X includes a butadiene unit, an isoprene unit, a 1,3-pentadiene unit, a 2,3-dimethyl-1,3-butadiene unit, and a 3-methyl-1,3-octadien unit. , Or 4-ethyl-1,3-hexadiene unit, and the like, but are not particularly limited.
  • the hydrogenated styrene-based copolymer In the production of the hydrogenated styrene-based copolymer, at least a part of the carbon-carbon double bond in the conjugated diene-based unit of the copolymer X needs to be saturated, and all of them need to be saturated. There is no.
  • the hydrogenated styrene-based copolymer may contain a conjugated diene-based unit contained in the copolymer X used for producing the hydrogenated styrene-based copolymer.
  • the copolymer X contains a butadiene unit as a conjugated diene-based unit
  • (a) hydrogen is not added to the hydrogenated styrene-based copolymer obtained by hydrogenating the copolymer X.
  • Butadiene units may be contained, and
  • (b-1) hydrogen may contain butylene units obtained by addition-polymerizing 1,2 to carbon-carbon double bonds of butadiene units, and (b-2) hydrogen. May contain ethylene units obtained by 1,4 addition polymerization of butadiene units of carbon-carbon double bonds.
  • the ratio of the conjugated diene-based unit to which hydrogen is added to the carbon-carbon double bond (hereinafter, "hydrogen") out of the total amount of the conjugated diene-based unit of the copolymer X used for production.
  • the addition rate is preferably 50% or more, more preferably 70% to 100%, and even more preferably 80% to 100%.
  • the hydrogenation rate of the hydrogenated styrene-based copolymer is within the above range, the hydrogenated styrene-based copolymer is likely to be present at the interface between the polypropylene-based resin and the AS copolymer, and the hydrogenated styrene-based copolymer is likely to be present.
  • the compatibilization effect of the copolymer tends to be improved.
  • the hydrogenation rate of the hydrogenated styrene-based copolymer may be 100%.
  • the hydrogenated styrene-based copolymer examples include styrene / ethylene / butylene / styrene block copolymer (SEBS), styrene / ethylene / propylene / styrene block copolymer (SEPS), and the like.
  • SEBS is composed of (a) a styrene block composed of only styrene units, (b) a butadiene block composed of only butadiene units, and (c) a styrene block composed of only styrene units, in this order. It is a copolymer obtained by hydrogenating a copolymer (copolymer X).
  • SEBS includes (a) a styrene block composed of only styrene units, (b) (b-1) 1, and a butylene unit formed by addition-polymerized butadiene units and (b). -2) A block in which 1,4 addition-polymerized butadiene units are hydrogenated and an ethylene unit is randomly bonded, and (c) a copolymer in which the styrene block is bonded in this order.
  • the block in which the butylene unit and the ethylene unit are randomly bonded may contain a butadiene unit.
  • SEPS consists of (a) a styrene block composed of only styrene units, (b) an isoprene block composed of only isoprene units, and (c) a styrene block composed of only styrene units, which are bonded in this order. It is a copolymer obtained by hydrogenating a copolymer (copolymer X). More specifically, SEPS includes (a) a styrene block composed of only styrene units, (b) a block in which ethylene units and propylene units are randomly bonded, which are hydrogenated with isoprene units, and (c).
  • the styrene block is a copolymer formed by bonding in this order.
  • the hydrogenated styrene-based copolymer preferably contains SEBS, and is particularly preferably SEBS, because it has the advantage of having relatively high strength.
  • the styrene unit content of the hydrogenated styrene-based copolymer (hereinafter, may be referred to as “styrene content”) is 5% by weight to 90% by weight in 100% by weight of the hydrogenated styrene-based copolymer. It is preferably 10% by weight to 85% by weight, more preferably 15% by weight to 80% by weight, and even more preferably 25% by weight to 55% by weight. According to this structure, there is an advantage that the compatibility between the polypropylene-based resin and the AS copolymer can be enhanced.
  • the styrene unit content of the hydrogenated styrene-based copolymer is 15% by weight or more in 100% by weight of the hydrogenated styrene-based copolymer, shrinkage and deformation after molding are more severe than those of the conventional product. There is a tendency to obtain reduced foam moldings.
  • the content of the hydrogenated styrene-based copolymer in the foamed particles is 3.0 parts by weight to 30.0 parts by weight with respect to 100 parts by weight of the polypropylene-based resin, and 4.0 parts by weight to 25.0 parts by weight.
  • 5.0 parts by weight to 20.0 parts by weight is more preferable, 5.0 parts by weight to 15.0 parts by weight is further preferable, and 5.0 parts by weight to 10.0 parts by weight is particularly preferable.
  • the content of the hydrogenated styrene-based copolymer is 3.0 parts by weight or more with respect to 100 parts by weight of the polypropylene-based resin, the phase of the polypropylene-based resin and the AS copolymer by the hydrogenated styrene-based copolymer. It has the advantage that the solubilization effect is fully exhibited.
  • the content of the hydrogenated styrene-based copolymer is 30.0 parts by weight or less with respect to 100 parts by weight of the polypropylene-based resin, (a) foamed particles having excellent foamability can be obtained, and (b) foamed particles can be obtained. It has the advantages that the rigidity of the foamed molded product to be molded is sufficient, and (c) a foamed molded product having further reduced shrinkage and deformation after molding as compared with the conventional product can be obtained.
  • the foamed particles include, as a resin component, a resin other than a polypropylene-based resin, an AS copolymer, and a hydrogenated styrene-based copolymer (other resins, etc.) as long as the effect according to the embodiment of the present invention is not impaired. It may be referred to.) Further may be included.
  • the other resins include (a) high-density polyethylene, medium-density polyethylene, low-density polyethylene, linear low-density polyethylene, linear ultra-low-density polyethylene, ethylene / vinyl acetate copolymer, ethylene / acrylic acid.
  • Copolymers and ethylene resins such as ethylene / methacrylic acid copolymers, (b) polystyrene, styrene / maleic anhydride copolymers, and styrene resins such as styrene / ethylene copolymers, (c) polyphenylene.
  • Polyphenylene ether-based resins such as ether and modified polyphenylene ether, polyolefin waxes such as (d) propylene / ⁇ -olefin wax, and (e) ethylene / propylene rubber, ethylene / butene rubber, ethylene / hexene rubber, ethylene / octene rubber, etc. Examples include olefin rubber.
  • the styrene resin and the polyphenylene ether resin are amorphous resins.
  • the content of other resins and the like in the foamed particles is preferably more than 0 parts by weight and 50 parts by weight or less, and more preferably more than 0 parts by weight and 30 parts by weight or less with respect to 100 parts by weight of the polypropylene-based resin. Further, the foamed particles do not have to contain other resins or the like. That is, the content of other resins and the like in the foamed particles may be 0 parts by weight.
  • the foamed particles may further contain an additive in addition to the resin component including the polypropylene-based resin, the AS copolymer and the hydrogenated styrene-based copolymer.
  • the additive include a colorant, a water-absorbent substance, a foaming nucleating agent, an antistatic agent, a flame retardant, an antioxidant, a light stabilizer, a crystal nucleating agent, a conductive agent, a lubricant and the like.
  • such an additive may be used in the production of the resin particles and contained in the resin particles, or may be directly added to the dispersion liquid in the foaming step described later.
  • the water-absorbent substance is a substance used for the purpose of increasing the amount of impregnated water in the resin particles in the production of the foamed particles.
  • foamability can be imparted to the resin particles.
  • the effect of the water-absorbent substance on imparting foamability to the resin particles becomes particularly remarkable when water is used as the foaming agent.
  • water-absorbent substance examples include glycerin, diglycerin, polyethylene glycol, C12 to C18 fatty alcohols (eg, pentaerythritol, cetyl alcohol, stearyl alcohol), melamine, and isocyanul.
  • examples thereof include acid, melamine-isocyanuric acid condensate, zinc borate and the like.
  • One kind of these water-absorbent substances may be used alone, or two or more kinds may be mixed and used. Further, when two or more kinds of water-absorbent substances are mixed and used, the mixing ratio may be appropriately adjusted according to the purpose.
  • Glycerin and polyethylene glycol (a) do not promote the miniaturization of the average bubble diameter of the foamed particles, and (b) have good compatibility with polypropylene-based resins. Therefore, among the above-mentioned water-absorbent substances, glycerin and / or polyethylene glycol are preferable.
  • the amount of the water-absorbent substance used in the production of the foamed particles in other words, the content of the water-absorbent substance in the foamed particles will be described.
  • the content of the water-absorbent substance in the foamed particles is 0.01 parts by weight to 1.00 parts by weight with respect to 100 parts by weight of the total amount of the polypropylene-based resin, the AS copolymer and the hydrogenated styrene-based copolymer. Is more preferable, and it is more preferably 0.05 part by weight to 0.70 part by weight, and further preferably 0.10 part by weight to 0.60 part by weight.
  • the content of the water-absorbent substance is (i) 0.01 parts by weight or more, the foaming effect of the water-absorbent substance can be sufficiently obtained, and (ii) 1.00 parts by weight or less. , There is no risk of the obtained foamed particles shrinking.
  • the foam nucleating agent is a substance that can be used in the production of the present foam particles and can become foam nuclei when the resin particles foam.
  • a foaming nucleating agent in other words, it is preferable that the foaming particles contain a foaming nucleating agent.
  • Examples of the effervescent nucleating agent that can be used in one embodiment of the present invention include silica (silicon dioxide), silicate, alumina, diatomaceous earth, calcium carbonate, magnesium carbonate, calcium phosphate, Nagaishi apatite, barium sulfate and the like.
  • Examples of the silicate include talc, magnesium silicate, kaolin, halloysite, decite, aluminum silicate, zeolite and the like.
  • one kind of these foam nucleating agents may be used alone, or two or more kinds may be mixed and used. Further, when two or more kinds of foam nucleating agents are mixed and used, the mixing ratio may be appropriately adjusted according to the purpose.
  • the amount of the foam nucleating agent used in the production of the foamed particles in other words, the content of the foamed nucleating agent in the foamed particles will be described. From the viewpoint of uniformity of average cell diameter, the content of the foam nucleating agent in the foam particles was 0. 005 parts by weight to 2.000 parts by weight are preferable, 0.010 parts by weight to 1.000 parts by weight are more preferable, and 0.030 parts by weight to 0.500 parts by weight are further preferable.
  • the total amount of additives used in the production of the foamed particles in other words, the total content of each additive in the foamed particles is more than 0 parts by weight and 10 parts by weight or less with respect to 100 parts by weight of the polypropylene resin. It is preferably more than 0 parts by weight and more preferably 5 parts by weight or less. Further, the foamed particles do not have to contain each additive. That is, the content of each additive in the foamed particles may be 0 parts by weight.
  • the foamed particles preferably have a foaming ratio of 15.0 to 50.0 times, more preferably 15.0 to 40.0 times, and 15.0 to 25.0 times. It is more preferable, and it is particularly preferable that it is 15.0 times to 20.0 times.
  • the foaming ratio of the foamed particles is (i) 15.0 times or more, a lightweight foamed molded product can be obtained with high production efficiency, and when (ii) 50.0 times or less, the obtained foamed molded product can be obtained. There is no risk of insufficient strength.
  • the “excellent foaming” foamed particles are intended to be foamed particles having a foaming ratio of 15.0 times or more of the foamed particles (one-stage foamed particles described later) formed by directly foaming the resin particles. ..
  • the expansion ratio of the expanded particles is calculated by the following methods (1) to (6): (1) The weight Gi of a certain amount of expanded particles is accurately measured to the unit of 0.001 g ((1). Round off the 4th digit after the decimal point); (2) Next, the entire amount of the foamed particles used for measuring the weight Gi is immersed in 100 mL of ethanol at 23 ° C. contained in a measuring cylinder; (3) Female. The volume y (cm 3 ) of the foamed particles is measured based on the increase in the liquid level position of the cylinder; (4) the weight Gi (g) of the foamed particles is divided by the volume yi (cm 3 ) of the foamed particles.
  • the foamed particles preferably have at least two melting peaks in the DSC curve obtained by the differential scanning calorimetry described below.
  • the amount of heat of melting obtained from the peak of melting on the high temperature side is referred to as "the amount of heat of melting on the high temperature side”
  • the amount of heat of melting obtained from the peak of melting on the low temperature side is referred to as "the amount of heat of melting on the low temperature side”.
  • the amount of heat of melting obtained from the hottest melting peak is the "heat of melting on the high temperature side”
  • the amount of heat of melting obtained from the other peaks of melting is "the amount of heat of melting on the low temperature side”.
  • the DSC ratio of the foamed particles is not particularly limited, but is preferably 10.0% to 50.0%, more preferably 20.0% to 40.0%, and 22.0% to 30%. It is more preferably 9.0%.
  • the DSC ratio of the foamed particles is 10.0% or more, there is an advantage that the foamed molded product obtained by molding the foamed particles has sufficient strength.
  • the DSC ratio of the foamed particles is 40% or less, there is an advantage that the foamed particles can be molded at a relatively low molding temperature.
  • the DSC ratio is intended to be the ratio of the heat of melting on the high temperature side to the total heat of melting calculated from the DSC curve of the foamed particles.
  • the DSC curve is obtained by using a differential scanning calorimeter (for example, DSC6200 type manufactured by Seiko Instruments). More specifically, in the present specification, the methods for measuring (calculating) the DSC ratio of foamed particles using a differential scanning calorimeter (for example, DSC6200 type manufactured by Seiko Instruments) are as follows (1) to (5). : (1) Weigh 5 mg to 6 mg of foamed particles; (2) Raise the temperature of the foamed particles from 40 ° C. to 220 ° C.
  • the heat quantity calculated from the region on the high temperature side surrounded by the line segment connecting the points representing the temperature of (a-2) and the DSC curve is defined as the heat quantity for melting on the high temperature side, and (b) (b-1) the maximum.
  • the amount of heat calculated from the region on the low temperature side surrounded by the line segment connecting the point and the point representing the temperature before the start of melting, (b-2) DSC curve, is defined as the amount of heat for melting on the low temperature side, and (c) the high temperature side.
  • the DSC ratio of the foamed particles is also a value that serves as a guide for the amount of crystals having a high melting point contained in the foamed particles. That is, the DSC ratio of the foamed particles is 10.0% to 50.0%, which indicates that the foamed particles contain a relatively large amount of crystals having a high melting point. Further, the DSC ratio of the foamed particles greatly contributes to the viscoelasticity of the resin particles and the foamed particles when the resin particles are foamed and when the foamed particles are expanded. That is, when the DSC ratio of the foamed particles is 10.0% to 50.0%, the resin particles and the foamed particles have excellent foamability when the resin particles are foamed and when the foamed particles are molded. And can exhibit swellability. As a result, the foamed particles have an advantage that it is possible to obtain a foamed molded product having excellent internal fusion property and mechanical strength such as compressive strength at a low molding pressure.
  • the conditions at the time of producing the present foamed particles are used. Etc.
  • Etc. can be adjusted. From the viewpoint of easy adjustment, a method of adjusting the foaming temperature, foaming pressure and / or holding time is preferable as a method of controlling the DSC ratio within a predetermined range.
  • the DSC ratio of the obtained foamed particles tends to be small, and conversely, when the foaming temperature is lowered, the DSC ratio of the obtained foamed particles tends to be large. This is because the amount of unmelted crystals contained in the foamed particles changes depending on the foaming temperature.
  • the foaming pressure is increased, the DSC ratio of the obtained foamed particles tends to be small, and conversely, when the foaming pressure is lowered, the DSC ratio of the obtained foamed particles tends to be large. This is because the foaming pressure changes the degree of plasticization, which in turn changes the amount of unmelted crystals contained in the foamed particles. Further, the longer the holding time, the larger the DSC ratio of the obtained foamed particles tends to be. This is because the amount of unmelted crystals contained in the foamed particles changes depending on the holding time.
  • the open cell ratio of the foamed particles is preferably 15.0% or less, more preferably 10.0% or less, more preferably 9.0% or less, and 8.0% or less. It is more preferably 7.0% or less, more preferably 6.0% or less, more preferably 5.0% or less, and 4.0% or less. Is more preferable, and 3.0% or less is particularly preferable.
  • the lower limit of the open cell ratio of the foamed particles is not particularly limited, and is, for example, 0.0% or more.
  • the cells are hardly foamed and shrunk during molding of the foamed particles, so that the foamed particles have an advantage of being excellent in moldability, and (b) obtained by using the foamed particles.
  • the foamed molded product it has an advantage that features such as shape arbitraryness, cushioning property, light weight, compressive strength and heat insulating property are more exhibited.
  • the open cell ratio of the foamed particles can be controlled by, for example, the amount of the AS copolymer used.
  • the open cell ratio of the foamed particles is determined by using an air comparative hydrometer [manufactured by Tokyo Science Co., Ltd., Model 1000] according to the method described in Procedure C (PROSEDURE C) of ASTM D2856-87. It is a value obtained by measurement. Specifically, the open cell ratio of the foamed particles is calculated by sequentially carrying out the following (1) to (4): (1) Volume Vc (cm 3 ) of the foamed particles using an air comparative gravimeter.
  • the method for measuring the volume Va as described above is also referred to as a submersion method.
  • the method for producing the foamed particles is not particularly limited, and a known production method can be appropriately used.
  • the method for producing the foamed particles includes a foaming step of foaming polypropylene-based resin particles, and the polypropylene-based resin particles include 100 parts by weight of the polypropylene-based resin and 5 weights of a copolymer containing an acrylonitrile unit and a styrene-based unit. It is preferable that the method comprises 60 parts by weight and 3 parts by weight to 30 parts by weight of the hydrogenated styrene-based copolymer.
  • the method for producing the foamed particles is not limited to the following production method.
  • a step of producing polypropylene-based resin particles (granulation step) can be performed.
  • polypropylene resin particles may be referred to as "resin particles”.
  • the granulation step 100 parts by weight of a polypropylene-based resin, 5 parts by weight to 60 parts by weight of a copolymer containing an acrylonitrile unit and a styrene-based unit, and 3 parts by weight to 30 parts by weight of a hydrogenated styrene-based copolymer are used. It can be said that this is a process of manufacturing resin particles containing the resin particles.
  • resin particles can be produced by the following methods (1) to (5): (1) polypropylene-based resin, AS copolymer and hydrogenated styrene-based copolymer, and If necessary, one or more selected from the group consisting of other resins and additives is blended to prepare a blend; (2) the blend is put into an extruder and the blend is melt-kneaded. The polypropylene-based resin composition is prepared; (3) the polypropylene-based resin composition is extruded from a die provided in the extruder; (4) the extruded polypropylene-based resin composition is cooled by passing it through water or the like.
  • the solidified polypropylene-based resin composition is shredded into a desired shape such as a columnar shape, an elliptical shape, a spherical shape, a cubic shape, a rectangular shape, or the like with a cutter.
  • the polypropylene-based resin composition melt-kneaded is extruded directly into water from a die provided in the extruder, and immediately after extrusion, the polypropylene-based resin composition is cut into particle shapes, cooled, and solidified. Is also good. By melt-kneading the blended product in this way, more uniform resin particles can be obtained.
  • the weight per grain of the resin particles obtained as described above is preferably 0.5 mg / grain to 3.0 mg / grain, and more preferably 0.7 mg / grain to 2.5 mg / grain.
  • the weight per grain of the resin particles is 0.5 mg / grain or more, the handleability of the resin particles tends to be improved, and when the weight is 3.0 mg / grain or less, the mold is filled in the in-mold foam molding step. There is a tendency for sex to improve.
  • the mode of the foaming step in the method for producing the foamed particles is not particularly limited as long as the resin particles can be foamed.
  • the foaming step is (A) A dispersion step of dispersing resin particles, an aqueous dispersion medium, a foaming agent, and if necessary, a dispersant and / or a dispersion aid in a container. (B) A temperature rise-boosting step in which the temperature inside the container is raised to a constant temperature and the pressure inside the container is raised to a constant pressure.
  • (C) A holding step of holding the temperature and pressure inside the container at a constant temperature and pressure
  • (D) It is preferable to include a discharge step of releasing one end of the container and discharging the dispersion liquid in the container to a region (space) having a pressure lower than the foaming pressure (that is, the pressure inside the container).
  • the process of producing the foamed particles from the resin particles in this way is referred to as a "one-stage foaming step", and the obtained foamed particles are referred to as “one-stage foamed particles”.
  • the amount of the polypropylene-based resin, AS copolymer, and hydrogenated styrene-based copolymer contained in the resin particles to be subjected to the foaming step is the polypropylene-based resin, AS copolymer, and hydrogenated styrene-based polymer in the obtained foamed particles. It is the amount of copolymer. Therefore, in the foaming step in the method for producing the foamed particles, 100 parts by weight of the polypropylene resin, 5 to 60 parts by weight of the copolymer containing the acrylonitrile unit and the styrene unit, and 3 weight of the hydrogenated styrene copolymer are used. It is preferable that the step is to foam the resin particles containing parts to 30 parts by weight.
  • the dispersion step can be said to be, for example, a step of preparing a dispersion liquid in which resin particles, a foaming agent, and, if necessary, a dispersant and / or a dispersion aid are dispersed in an aqueous dispersion medium.
  • the container used in the dispersion step is not particularly limited, but a container that can withstand the foaming temperature and foaming pressure described later is preferable.
  • a container that can withstand the foaming temperature and foaming pressure described later is preferable.
  • a pressure-resistant container is preferable, and an autoclave type pressure-resistant container is more preferable.
  • the aqueous dispersion medium is not particularly limited as long as it can uniformly disperse resin particles, a foaming agent, and the like.
  • the aqueous dispersion medium include (a) a dispersion medium obtained by adding methanol, ethanol, ethylene glycol, glycerin and the like to water, and (b) water such as tap water and industrial water.
  • the aqueous dispersion medium includes RO water (water purified by the reverse osmosis membrane method), distilled water, deionized water (water purified by an ion exchange resin), etc. It is preferable to use pure water, ultrapure water, or the like.
  • the amount of the aqueous dispersion medium used is not particularly limited, but is preferably 100 parts by weight to 400 parts by weight with respect to 100 parts by weight of the resin particles.
  • the amount of the aqueous dispersion medium used is (a) 100 parts by weight or more, there is no possibility that the stability of the dispersion liquid is deteriorated (in other words, the dispersion of the resin particles is good), and (b) 400 parts by weight or less. If this is the case, there is no risk that the productivity of the foamed particles will decrease.
  • the effervescent agent examples include (a) (a-1) an inorganic gas such as nitrogen, carbon dioxide and air (a mixture of oxygen, nitrogen and carbon dioxide), and (a-2) an inorganic effervescent agent such as water; (B) (b-1) Saturated hydrocarbons having 3 to 5 carbon atoms such as propane, normal butane, isobutane, normal pentane, isopentan, neopentane, and (b-2) ethers such as dimethyl ether, diethyl ether, and methyl ethyl ether.
  • (B-3) Organic foaming agents such as monochloromethane, dichloromethane, halogenated hydrocarbons such as dichlorodifluoroethane; and the like.
  • the foaming agent at least one selected from the group consisting of the above-mentioned inorganic foaming agent and organic foaming agent can be used. When two or more kinds of foaming agents are mixed and used, the mixing ratio may be appropriately adjusted according to the purpose. From the viewpoint of environmental load and foaming power, the inorganic foaming agent is preferable as the foaming agent among the above-mentioned foaming agents.
  • carbon dioxide is preferable among the inorganic foaming agents because it has a moderately high plasticizing effect and easily improves the foamability of the foamed particles in the production of the foamed particles.
  • the amount of the foaming agent used is not particularly limited, and may be appropriately used according to (a) the type of foaming agent and / or (b) the desired expansion ratio of the foamed particles.
  • the amount of the foaming agent used is, for example, preferably 1 part by weight to 10000 parts by weight, more preferably 1 part by weight to 5000 parts by weight, still more preferably 1 part by weight to 1000 parts by weight, based on 100 parts by weight of the resin particles.
  • foamed particles having a suitable density can be obtained.
  • the amount of the foaming agent used is 10,000 parts by weight or less with respect to 100 parts by weight of the resin particles, the effect according to the amount of the foaming agent used can be obtained, so that no economic waste occurs.
  • the amount of the foaming agent used may be, for example, 1 part by weight to 100 parts by weight or 1 part by weight to 10 parts by weight with respect to 100 parts by weight of the resin particles.
  • the water in the dispersion liquid in the container can be used as the foaming agent.
  • the resin particles contain a water-absorbent substance in advance. As a result, the resin particles can easily absorb the water of the dispersion liquid in the container, and as a result, the water can be easily used as a foaming agent.
  • a dispersant in the method for producing the foamed particles.
  • the dispersant include inorganic substances such as calcium tertiary phosphate, magnesium tertiary phosphate, basic magnesium carbonate, calcium carbonate, barium sulfate, kaolin, talc, clay, aluminum oxide, titanium oxide, and aluminum hydroxide.
  • the dispersant may be used alone, or two or more types may be mixed and used. Further, when two or more kinds of dispersants are mixed and used, the mixing ratio may be appropriately adjusted according to the purpose.
  • the amount of the dispersant used in the dispersion liquid used in one embodiment of the present invention is preferably 0.01 parts by weight to 3.00 parts by weight, preferably 0.05 parts by weight to 2 parts by weight with respect to 100 parts by weight of the resin particles. .00 parts by weight is more preferable, and 0.10 parts by weight to 1.00 parts by weight is further preferable.
  • the amount of the dispersant used is (a) 0.01 parts by weight or more, there is no risk of causing poor dispersion of the resin particles, and (b) when it is 3.00 parts by weight or less, the obtained foamed particles are used. During in-mold foam molding, there is no risk of causing poor fusion between the foamed particles.
  • a dispersion aid is used in order to (a) improve the effect of reducing the coalescence of the resin particles and / or (b) improve the stability of the dispersion liquid in the container. It is preferable to do so.
  • the dispersion aid include anionic surfactants.
  • the anionic surfactant include sodium alkylbenzene sulfonate such as sodium dodecylbenzene sulfonate, sodium alkane sulfonate, sodium alkyl sulfonate, sodium alkyl diphenyl ether disulfonate, sodium ⁇ -olefin sulfonate and the like.
  • One type of these dispersion aids may be used alone, or two or more types may be mixed and used. Further, when two or more kinds of dispersion aids are mixed and used, the mixing ratio may be appropriately adjusted according to the purpose.
  • the amount of the dispersion aid used in the dispersion liquid used in one embodiment of the present invention is preferably 0.001 part by weight to 0.500 part by weight, preferably 0.001 part by weight, based on 100 parts by weight of the resin particles. It is more preferably from parts by weight to 0.200 parts by weight, and even more preferably from 0.010 parts by weight to 0.200 parts by weight. When the amount of the dispersion aid used is within the above range, there is no risk of causing poor dispersion of the resin particles.
  • the temperature rise-pressurization step is preferably performed after the dispersion step, and the holding step is preferably performed after the temperature rise-pressurization step.
  • a constant temperature in the temperature raising-pressurizing step and the holding step may be referred to as a foaming temperature
  • a constant pressure may be referred to as a foaming pressure.
  • the foaming temperature varies depending on the types of polypropylene-based resin, AS copolymer and hydrogenated styrene-based copolymer, the type of foaming agent, the apparent density of desired foamed particles, etc., and cannot be unconditionally specified.
  • the foaming temperature is (i) (a) a mixture of polypropylene-based resin, AS copolymer and hydrogenated styrene-based copolymer, (b) polypropylene-based resin composition, or (c) melting point of resin particles-20.0.
  • the temperature is preferably from ° C to + 10.0 ° C, and is preferably (ii) (a) a mixture of a polypropylene-based resin, an AS copolymer and a hydrogenated styrene-based copolymer, (b) a polypropylene-based resin composition, or (c). )
  • the melting point of the resin particles is more preferably -15.0 ° C to + 8.0 ° C, and (iii) (a) a mixture of a polypropylene-based resin, an AS copolymer and a hydrogenated styrene-based copolymer, (b). )
  • the polypropylene-based resin composition or (c) the resin particles has a melting point of -10.0 ° C to a melting point of + 6.0 ° C, which is more preferable.
  • the foaming pressure is preferably 1.0 MPa (gauge pressure) to 10.0 MPa (gauge pressure), more preferably 2.0 MPa (gauge pressure) to 5.0 MPa (gauge pressure), and 2.5 MPa (gauge pressure) to 3. 5.5 MPa (gauge pressure) is more preferable.
  • the foaming pressure is 1.0 MPa (gauge pressure) or more, foamed particles having a suitable density can be obtained.
  • the time (holding time) for holding the dispersion liquid in the container near the foaming temperature and the foaming pressure is not particularly limited.
  • the holding time is preferably 10 to 60 minutes, more preferably 12 to 55 minutes, and even more preferably 15 to 50 minutes.
  • a sufficient amount of unmelted crystals polypropylene resin crystals
  • the shrinkage of the obtained foamed particles and / or the increase in the open cell ratio can be reduced.
  • the holding time is 60 minutes or less, there is no excessive amount of unmelted crystals, so that there is an advantage that the foamed particles can be molded at a low molding temperature.
  • the release step is carried out after (a) a temperature rise-pressurization step when the holding step is not carried out, and (b) after the holding step when the holding step is carried out.
  • the release step allows the resin particles to be foamed, resulting in foamed particles.
  • the "region below the foaming pressure” is intended as “the region under the pressure below the foaming pressure” or “the space under the pressure below the foaming pressure”, and the "atmosphere at a pressure lower than the foaming pressure”. It can also be said to be “below.”
  • the region having a lower pressure than the foaming pressure is not particularly limited as long as the pressure is lower than the foaming pressure, and may be, for example, a region under atmospheric pressure.
  • the discharge step when the dispersion liquid is discharged to a region lower than the foaming pressure, the dispersion liquid is passed through an open orifice having a diameter of 1 mm to 5 mm for the purpose of adjusting the flow rate of the dispersion liquid and reducing the variation in the expansion ratio of the obtained foamed particles. Can also be released. Further, for the purpose of improving foamability, the low pressure region (space) may be filled with saturated steam.
  • Examples of the method 2 include a method including the following (a1) to (a3) in order: (a1) One-stage foamed particles having a foaming ratio of 2.0 to 35.0 times in the one-stage foaming step. Manufacture; (a2) The one-stage foamed particles are placed in a pressure-resistant container and pressure-treated with nitrogen, air, carbon dioxide, etc. at 0.2 MPa (gauge pressure) to 0.6 MPa (gauge pressure) to perform one-stage. The pressure inside the foamed particles (hereinafter, may be referred to as "internal pressure") is made higher than the normal pressure; (a3) Then, a method of heating the one-stage foamed particles having an increased internal pressure with steam or the like to further foam them.
  • the step of increasing the foaming ratio of the one-stage foamed particles as in Method 2 is called a “two-stage foaming step", and the polypropylene-based resin foamed particles obtained by the method of Method 2 are called “two-stage foamed particles”.
  • the pressure of water vapor for heating the one-stage foamed particles is 0.03 MPa (gauge pressure) to 0.20 MPa (gauge pressure) in consideration of the expansion ratio of the two-stage foamed particles. It is preferable to adjust the gauge pressure).
  • the pressure of water vapor in the two-stage foaming step is 0.03 MPa (gauge pressure) or more, the foaming ratio tends to improve, and when it is 0.20 MPa (gauge pressure) or less, the obtained two-stage foamed particles are used. Is less likely to coalesce. When the two-stage foamed particles are coalesced together, the obtained two-stage foamed particles may not be available for subsequent in-mold foam molding.
  • the internal pressure of the one-stage foamed particles obtained by impregnating the one-stage foamed particles with nitrogen, air, carbon dioxide, etc. may be appropriately changed in consideration of the expansion ratio of the two-stage foamed particles and the water vapor pressure in the two-stage foaming step. desirable.
  • the internal pressure of the one-stage foamed particles is preferably 0.15 MPa (absolute pressure) to 0.60 MPa (absolute pressure), more preferably 0.20 MPa (absolute pressure) to 0.60 MPa (absolute pressure), and 0.30 MPa (absolute pressure). Pressure) to 0.60 MPa (absolute pressure) is more preferable.
  • Polypropylene resin foam molded product The polypropylene-based resin foam molded article according to the embodiment of the present invention is described in [1.
  • Polypropylene-based resin foamed particles] is a foamed molded product obtained by molding the polypropylene-based resin foamed particles described in the section.
  • the polypropylene-based resin foam molded article according to the embodiment of the present invention is described in [1. It can be said that the polypropylene-based resin foamed particles described in the section [Polypropylene-based resin foamed particles] are included.
  • the present foamed molded product is formed by molding polypropylene-based resin foam particles obtained by the method for producing the present foam particles (for example, the production method described in the above-mentioned ⁇ Production method for producing polypropylene-based resin foam particles>).
  • polypropylene-based resin foam particles obtained by the method for producing the present foam particles
  • it can be said to be a foam molded product, it can also be said to be a foam molded product containing polypropylene-based resin foam particles obtained by the method for producing the present foam particles.
  • the present foam molded product is described in the above [1.
  • polypropylene resin foam molded product according to the embodiment of the present invention may be referred to as the "present foam molded product”.
  • the foam molded product has the above-mentioned structure, it has an advantage that there is almost no shrinkage or deformation after molding.
  • shrinkage factor ((L1-L0) ⁇ 100) / L0.
  • the shrinkage of the foam molded product is preferably 1.2% or less, more preferably 1.0% or less, further preferably 0.8% or less, and 0.6% or less. It is particularly preferable to have. It can be said that the foam molded product having a shrinkage ratio of 1.2% or less has good dimensional stability because it is intended that the foamed molded product obtained by production is unlikely to have dimensional variation.
  • the foamed particles that can provide a foamed molded product having good dimensional stability, and the foamed molded product have an advantage that they can be suitably used in the field of insert molding that is integrally molded with other materials such as metal.
  • FIG. 1 is a schematic view of a foam molded product 100 used for evaluating the amount of deformation.
  • the foam molded body 100 is manufactured using a mold having a partition plate in the center of the mold (length direction 350 mm ⁇ lateral direction 320 mm ⁇ thickness direction (moving mold drive direction) 180 mm).
  • the X direction can be said to be the thickness direction of the foam molded product 100, and can also be said to be the movable drive direction.
  • the Y direction can be said to be the longitudinal direction of the foam molded product 100, and is a direction that intersects the X direction perpendicularly.
  • the Z direction can be said to be the lateral direction of the foam molded product 100, and is a direction that intersects each of the X direction and the Y direction perpendicularly.
  • the dimensions (lengths) of the two ends in the longitudinal direction in the Z direction are K1 and K2, respectively, and the dimension in the Z direction of the central portion in the longitudinal direction is K3.
  • the amount of deformation of the foam molded product is preferably 14.0 mm or less, more preferably 13.0 mm or less, more preferably 12.0 mm or less, and more preferably 11.0 mm or less. It is preferably 10.0 mm or less, more preferably 9.0 mm or less, more preferably 8.0 mm or less, more preferably 7.0 mm or less, and 6.0 mm or less. Is more preferable, and 5.0 mm or less is particularly preferable. It can be said that the foamed molded product having a deformation amount of 14.0 mm or less has good dimensional stability because it is intended that the foamed molded product obtained by manufacturing is less likely to have dimensional variation.
  • the method for producing the foam molded product is not particularly limited, and a known method can be applied.
  • a method for producing the present foam molded product the above-mentioned [1. Includes a step of in-mold foam molding of the main foamed particles described in the item [Polypropylene resin foamed particles] or the foamed particles obtained by the production method described in the above item ⁇ Method for producing polypropylene-based resin foamed particles>. Is preferable.
  • Specific embodiments of the method for producing the present foam molded product include, for example, a production method (in-mold foam molding method) including the following (b1) to (b6) in order, but the present invention is not limited to such a production method.
  • a production method in-mold foam molding method
  • the present invention is not limited to such a production method.
  • (B1) A mold composed of a fixed mold that cannot be driven and a movable mold that can be driven is mounted on the in-mold foam molding machine.
  • the fixed type and the mobile type can be formed inside the fixed type and the mobile type by driving the mobile type toward the fixed type (the operation may be referred to as "mold closing");
  • (B2) Drive the mobile mold toward the fixed mold so that a slight gap (also referred to as cracking) is formed so that the fixed mold and the mobile mold are not completely closed.
  • (B3) Foamed particles are filled into the molding space formed inside the fixed mold and the mobile mold, for example, through a filling machine; (B4) Drive the mobile type so that the fixed type and the mobile type are completely closed (that is, completely closed); (B5) After preheating the mold with steam, the mold is heated on one side and the other side with steam, and then the mold is heated on both sides with steam to perform in-mold foam molding; (B6) The foamed molded product in the mold is taken out from the mold and dried (for example, dried at 75 ° C.) to obtain a foamed molded product.
  • (B3-1) As a method of filling the foamed particles in the molding space, the following methods (b3-1) to (b3-4) can be mentioned: (B3-1)
  • the foamed particles (including the above-mentioned two-stage foamed particles, the same applies hereinafter) are pressure-treated with an inorganic gas in a container, the foamed particles are impregnated with the inorganic gas, and a predetermined internal pressure of the foamed particles is applied.
  • a method of filling the molding space with the foamed particles after the application (B3-2) A method of filling a molding space with foamed particles and then compressing the volume in the mold so as to reduce the volume by 10% to 75%; (B3-3) A method of compressing foamed particles with gas pressure and filling the molding space; (B3-4) A method of filling a molding space with foamed particles without any particular pretreatment.
  • At least one selected from the group consisting of air, nitrogen, oxygen, carbon dioxide, helium, neon, argon and the like can be used as the inorganic gas in the method (b3-1). .. Among these inorganic gases, air and / or carbon dioxide are preferable.
  • the internal pressure of the foamed particles in the method (b3-1) is preferably 0.10 MPa (absolute pressure) to 0.30 MPa (absolute pressure), and 0.11 MPa (absolute pressure) to 0. 25 MPa (absolute pressure) is preferable.
  • the temperature inside the container when the foamed particles are impregnated with the inorganic gas by the method (b3-1) is preferably 10 ° C. to 90 ° C., more preferably 40 ° C. to 90 ° C. ..
  • One embodiment of the present invention may have the following configuration.
  • the styrene unit content of the hydrogenated styrene-based copolymer is 15% by weight to 80% by weight in 100% by weight of the hydrogenated styrene-based copolymer, any of [1] to [3].
  • the polypropylene-based resin foamed particles according to one.
  • a polypropylene-based resin foam molded product obtained by molding the polypropylene-based resin foamed particles according to any one of [1] to [5].
  • the polypropylene-based resin particles have a foaming step of foaming the polypropylene-based resin particles, and the polypropylene-based resin particles are composed of 100 parts by weight of the polypropylene-based resin and 5 to 60 parts by weight of a copolymer containing an acrylonitrile unit and a styrene-based unit.
  • a method for producing polypropylene-based resin foamed particles which comprises 3.0 parts by weight to 30.0 parts by weight of a hydrogenated styrene-based copolymer.
  • the styrene unit content of the hydrogenated styrene-based copolymer is any one of [7] to [9], which is 15% by weight to 80% by weight in 100% by weight of the hydrogenated styrene-based copolymer.
  • the melting point of the polypropylene-based resin was a value obtained by measuring by the DSC method using a differential scanning calorimeter (manufactured by Seiko Instruments Co., Ltd., DSC6200 type).
  • the specific operation procedure was as follows (1) to (4): (1) The temperature of the polypropylene-based resin 5 mg to 6 mg was raised from 40.0 ° C to 220 at a heating rate of 10.0 ° C / min. The polypropylene-based resin was melted by raising the temperature to 0 ° C.; (2) Then, the temperature of the melted polypropylene-based resin was lowered from 220.0 ° C.
  • the polypropylene-based resin was crystallized by lowering the temperature to ° C; (3), and then the temperature of the crystallized polypropylene-based resin was further increased from 40.0 ° C to 220 at a heating rate of 10.0 ° C / min. The temperature was raised to 0.0 ° C.; (4) The temperature of the peak (melting peak) of the DSC curve of the polypropylene-based resin obtained at the time of the second temperature rise (that is, at the time of (3)) was the melting point of the polypropylene-based resin. And said.
  • the temperature of the peak (melting peak) having the maximum heat of fusion is used.
  • the melting point of the polypropylene resin was used.
  • the glass transition temperature (Tg) of the AS polymer is the following (1) to (5) in accordance with JIS-K-7121 using a differential scanning calorimeter [DSC6200 type manufactured by Seiko Instruments Co., Ltd.]. ): (1) 5 mg of AS polymer was weighed; (2) the temperature of the AS polymer was raised from room temperature to 250 ° C. at 10 ° C./min under a nitrogen atmosphere. (3) The temperature of the heated AS polymer was lowered from 250 ° C. to room temperature at 10 ° C./min; (4) The temperature of the AS polymer was again lowered from room temperature to 250 ° C. at 10 ° C./min. (5) The temperature of the peak (melting peak) of the DSC curve of the AS polymer obtained at the time of the second temperature rise (that is, at the time of (4)) was defined as Tg of the AS polymer. ..
  • MFR of polypropylene resin and AS copolymer The MFR of the polypropylene resin or AS copolymer was measured under the following conditions using the MFR measuring instrument described in JIS K7210: 1999: the diameter of the orifice was 2.0959 ⁇ 0. 005 mm ⁇ , orifice length 8,000 ⁇ 0.025 mm, load 2.16 kgf, and temperature 230 ° C (230 ⁇ 0.2 ° C).
  • the method for measuring the expansion ratio of the expanded particles was as follows (1) to (6): (1) The weight Gi of a certain amount of expanded particles (one-stage expanded particles or two-stage expanded particles) was 0.001 g. (Rounded to the 4th digit after the decimal point); (2) Next, the entire amount of the foamed particles used for measuring the weight Gi was immersed in 100 mL of water at 23 ° C contained in a measuring cylinder.
  • the volume y (cm 3 ) of the foamed particles was measured based on the increase in the liquid level position of the measuring cylinder; (4) the weight Gi (g) of the foamed particles was measured as the volume y (g) of the foamed particles.
  • the apparent density di (g / L) of the foamed particles was calculated by dividing by cm 3 ) and converting this into g / L units; (5) Instead of the foamed particles, the resin particles used for producing the foamed particles were used.
  • the density ds (g / L) of the resin particles was calculated by performing the same operations as in (1) to (4); (6)
  • the foamability of the foamed particles was evaluated by the foaming ratio of the one-stage foamed particles obtained by performing the one-stage foaming step under the same conditions.
  • the evaluation criteria are as follows. ⁇ (Good): The expansion ratio of the one-stage expanded particles is 15.0 times or more. X (defective): The expansion ratio of the one-stage expanded particles is less than 15.0 times.
  • the expansion ratio of the expanded particles is affected by the DSC ratio of the expanded particles.
  • the foamed particles are produced by adjusting the foaming temperature or the like so that the DSC ratio of the foamed particles is low, the foamed particles having a high foaming ratio tend to be obtained. Therefore, when comparing the foaming ratios of different foamed particles, it is necessary to compare the foaming ratios in consideration of the influence of the DSC ratio of the foamed particles. That is, when comparing the expansion ratios between different foamed particles, the expansion ratios of the expanded particles can be compared relatively accurately by producing the expanded particles so that the DSC ratios are close to each other.
  • DSC ratio of foamed particles In the measurement (calculation) of the DSC ratio of the foamed particles, a differential scanning calorimeter (DSC6200 type manufactured by Seiko Instruments) was used. The method for measuring (calculating) the DSC ratio of foamed particles using a differential scanning calorimeter was as follows (1) to (5): (1) 5 mg to 6 mg of foamed particles were weighed; (2). The temperature of the foamed particles was raised from 40 ° C. to 220 ° C. at a heating rate of 10 ° C./min to melt the foamed particles; (3) DSC curve of the foamed particles obtained in the step (2) above.
  • the maximum point between the hottest melting peak and the melting peak next to the melting peak (on the low temperature side) and the point representing the temperature before the start of melting are connected by a straight line, and (b) the above.
  • a straight line connects the maximum point and the point representing the temperature after melting;
  • the amount of heat calculated from the region on the low temperature side surrounded by the minute and (b-2) DSC curve is taken as the amount of heat for melting on the low temperature side, and the sum of (c) the amount of heat for melting on the high temperature side and the amount of heat for melting on the low temperature side is total melting.
  • the mold used for measuring the shrinkage rate may be referred to as a shrinkage rate evaluation mold.
  • the mold used for measuring the deformation amount may be referred to as a deformation amount evaluation mold.
  • Example 1 (Preparation of polypropylene resin particles) 100 parts by weight (10 kg) of polypropylene resin, 12 parts by weight (1.2 kg) of AS copolymer 1, 7.0 parts by weight (700 g) of hydrogenated styrene polymer 1, as a foam nucleating agent. 0.050 parts by weight (5 g) of talc and 0.2 parts by weight (20 g) of glycerin as a water-absorbent substance were dry-blended.
  • the obtained blend was put into a twin-screw extruder [TEM26-SX manufactured by Toshiba Machine Co., Ltd.] and melt-kneaded at a resin temperature of 250 ° C.
  • the melt-kneaded polypropylene-based resin composition was extruded into a strand shape through a die having a circular hole attached to the tip of the extruder.
  • the extruded polypropylene-based resin composition was cooled with water and then cut with a cutter to obtain columnar resin particles (1.2 mg / grain).
  • the temperature inside the pressure-resistant airtight container was heated to a foaming temperature of 151.0 ° C.
  • carbon dioxide was additionally press-fitted into the pressure-resistant airtight container, and the pressure inside the pressure-resistant airtight container was increased to a foaming pressure of 3.2 MPa (gauge pressure) (heating-pressurizing step).
  • the valve at the bottom of the airtight container is opened, and the dispersion liquid is foamed under atmospheric pressure through an orifice having a diameter of 3.6 mm.
  • Foamed particles one-stage foamed particles
  • the one-stage foamed particles in the foaming machine are heated with steam of 0.06 MPa (gauge pressure) for 30 seconds to further foam the one-stage foamed particles (two-stage foaming), and the foamed particles (two-stage foamed particles). ) was obtained.
  • the obtained foamed particles (two-stage foamed particles) were put into a pressure-resistant airtight container. Air is introduced into the pressure-resistant airtight container, and the two-stage foamed particles in the pressure-resistant airtight container are impregnated with pressurized air to apply 0.20 MP (absolute pressure) internal pressure of the foamed particles (absolute pressure) to the two-stage foamed particles. did.
  • the two-stage foamed particles impregnated with air were subjected to 0.30 MPa (0.30 MPa) using a molding machine (polypropylene mold in-mold foam molding machine manufactured by Daisen Co., Ltd.) and a shrinkage rate evaluation mold and a deformation amount evaluation mold.
  • a foam-molded article was obtained by heat-molding with steam of (gauge pressure). After each of the obtained foam molded products was left at room temperature for 1 hour, it was cured and dried in a constant temperature room at 75 ° C. for 12 hours, and then left again at room temperature for 4 hours. Then, the shrinkage rate and the amount of deformation of the obtained foam molded product were evaluated by the above-mentioned method. The results are shown in Table 1.
  • Examples 2 to 7, Comparative Examples 1 to 9 Foamed particles and foamed compacts were obtained by the same method as in Example 1 except that the type of each material, the amount of each material, and / or each production condition were changed as shown in Table 1. The physical characteristics of the obtained foamed particles and foamed molded product were measured and evaluated. The results are shown in Table 1.
  • the polypropylene-based resin foamed particles according to the embodiment of the present invention can provide a polypropylene-based resin foamed molded product having excellent foamability and hardly shrinking or deforming after molding.
  • the polypropylene-based resin foam molded product can be suitably used for various applications such as cushioning packaging materials, physical distribution materials, heat insulating materials, civil engineering and building materials, and automobile materials.

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

La présente invention aborde le problème de la fourniture de particules de mousse de résine de polypropylène qui (a) peuvent fournir un article moulé en mousse de résine de polypropylène qui ne présente pratiquement pas de retrait ou de déformation post-moulage, et (b) présentent d'excellentes caractéristiques de moussage. Les particules de mousse de résine de polypropylène contiennent des quantités prescrites des éléments suivants : une résine de polypropylène ; un copolymère contenant une unité acrylonitrile et une unité styrénique ; et un copolymère styrénique hydrogéné.
PCT/JP2021/048735 2021-01-08 2021-12-28 Particules de mousse de résine de polypropylène et article moulé en mousse de résine de polypropylène WO2022149538A1 (fr)

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JP2011529105A (ja) * 2008-03-13 2011-12-01 ビーエーエスエフ ソシエタス・ヨーロピア ポリオレフィン／スチレンポリマー混合物に基づく弾性成形フォームビーズ
JP2013542302A (ja) * 2010-11-11 2013-11-21 ビーエーエスエフ ソシエタス・ヨーロピア 発泡性の改善された発泡性熱可塑性ビーズの製造方法
JP2016044199A (ja) * 2014-08-20 2016-04-04 株式会社ジェイエスピー 発泡性複合樹脂粒子
WO2018016399A1 (fr) * 2016-07-19 2018-01-25 株式会社カネカ Particules pré-expansées de résine à base de polypropylène, et procédé de fabrication de celles-ci

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4824500B1 (fr) * 1969-10-01 1973-07-21
JPH1087926A (ja) * 1996-09-11 1998-04-07 Sumika A B S Latex Kk 発泡性軟質樹脂組成物
JP2002506105A (ja) * 1998-03-11 2002-02-26 ザ ダウ ケミカル カンパニー α−オレフィン／芳香族ビニルまたはビニリデンおよび／またはヒンダード脂肪族ビニルまたはビニリデンインターポリマーから製造される形状記憶性を有する構造体および二次加工品
JP2005068289A (ja) * 2003-08-25 2005-03-17 Nagase & Co Ltd 自動車用内装部材およびその製造方法
US20070112081A1 (en) * 2003-12-12 2007-05-17 Basf Aktiengensellschaft Moldable-foam moldings composed of expandable styrene polymers and mixtures with thermoplastic polymers
JP2011058008A (ja) * 2006-02-28 2011-03-24 Sekisui Plastics Co Ltd 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及びスチレン改質ポリプロピレン系樹脂発泡成形体の製造方法
JP2011529105A (ja) * 2008-03-13 2011-12-01 ビーエーエスエフ ソシエタス・ヨーロピア ポリオレフィン／スチレンポリマー混合物に基づく弾性成形フォームビーズ
JP2010254930A (ja) * 2009-04-28 2010-11-11 Furukawa Electric Co Ltd:The 発泡成形体およびその製造方法
JP2013542302A (ja) * 2010-11-11 2013-11-21 ビーエーエスエフ ソシエタス・ヨーロピア 発泡性の改善された発泡性熱可塑性ビーズの製造方法
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