WO2023042701A1 - プロピレン系樹脂組成物およびその用途 - Google Patents

プロピレン系樹脂組成物およびその用途 Download PDF

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WO2023042701A1
WO2023042701A1 PCT/JP2022/033285 JP2022033285W WO2023042701A1 WO 2023042701 A1 WO2023042701 A1 WO 2023042701A1 JP 2022033285 W JP2022033285 W JP 2022033285W WO 2023042701 A1 WO2023042701 A1 WO 2023042701A1
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propylene
mass
copolymer
resin composition
based resin
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PCT/JP2022/033285
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English (en)
French (fr)
Japanese (ja)
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晃 箕輪
蒼 瀬田
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株式会社プライムポリマー
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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
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a propylene-based resin composition and an injection foam-molded article suitable for obtaining a foam-molded article having a uniform cell diameter, good appearance, and excellent surface impact resistance.
  • Foam molding is one of the important molding methods for polypropylene.
  • Various molded articles obtained by extrusion foam molding and injection foam molding are used in a wide range of applications, taking advantage of their excellent properties such as heat insulation, sound insulation, cushioning, and energy absorption. It is generally known that the higher the expansion ratio of the foam, the better the cushioning and heat insulating properties, and the higher the open cell ratio, the better the sound absorption and the lighter the weight.
  • foamed molded products have significantly lower surface impact performance and are prone to appearance defects peculiar to foam such as swirl marks. Goods are in demand in the market.
  • Patent Document 1 a method of blending an ethylene/ ⁇ -olefin copolymer having a high melt tension and an olefin polymer resin having a low melt tension with a polypropylene resin
  • Patent Document 2 polypropylene
  • An object of the present invention is to obtain a propylene-based resin composition suitable for obtaining a foam molded article having a uniform cell diameter, good appearance, and excellent surface impact resistance.
  • the intrinsic viscosity [ ⁇ ] of the propylene/ethylene copolymer portion specified as the n-decane soluble portion (Dsol) at 23°C in tetralin at 135°C is 4.0 to 9.0 dl/g. 5 to 22% by mass of the propylene/ethylene copolymer (a1) specified as the n-decane soluble portion and 78 to 95% by mass of the propylene homopolymer (a2), provided that (a1 )+(a2) is 100% by mass.
  • a1 )+(a2) is 100% by mass.
  • the injection foam molded product obtained by injection foam molding the propylene-based resin composition of the present invention has a uniform cell diameter, a good appearance, and excellent surface impact resistance. It can be suitably used for various applications such as electric appliances and building materials.
  • FIG. 1 is a schematic diagram of injection foam molded articles obtained in Examples and Comparative Examples.
  • FIG. 1 is a schematic diagram of injection foam molded articles obtained in Examples and Comparative Examples.
  • the propylene-based polymer (A) which is one of the components contained in the propylene-based resin composition of the present invention, is a propylene-ethylene copolymer portion specified as n-decane soluble portion (Dsol) at 23°C
  • Intrinsic viscosity [ ⁇ ] in tetralin at 135°C is in the range of 4.0 to 9.0 dl/g, preferably 5.0 to 8.0 dl/g, more preferably 6.0 to 8.0 dl/g 5 to 22% by mass, preferably 5 to 15% by mass, more preferably 5 to 13% by mass of the propylene/ethylene copolymer (a1) specified as the n-decane soluble portion, and a propylene homopolymer (a2) is 78 to 95% by mass, preferably 85 to 95% by mass, more preferably 87 to 95% by mass [provided that the total amount of (a1) + (a2) is 100% by mass.
  • MFR measured at a temperature of 230 ° C. and a load of 2.16 kg according to ASTM D-1238 is 70 to 150 g / 10 minutes, preferably 73 to 130 g / 10 minutes, more preferably 75 to 110 g / 10 minutes in the range.
  • the propylene-based polymer (A) according to the present invention may be used alone or in combination of two or more.
  • a propylene-based polymer having a propylene/ethylene copolymer (a1) content of less than 5% by mass may deteriorate the impact resistance of a molded article obtained from the composition, while the content exceeds 22% by mass. Since the propylene-based polymer significantly lowers the viscosity of the composition, there is a possibility that the resulting molded article may have poor appearance.
  • a propylene-based polymer (A) in which the content of the propylene/ethylene copolymer (a1) satisfies the above range has a good appearance and excellent surface impact resistance.
  • the resulting composition has an optimum viscosity range. It is possible to obtain a molded article having a cell diameter, a good appearance, and excellent surface impact resistance.
  • a propylene-based polymer (A) with an MFR of less than 70 g/10 minutes has a high viscosity, so shear heat generation during resin filling increases. As a result, the amount of gas generated increases, and there is a risk that the appearance of the obtained molded article will deteriorate.
  • the MFR exceeds 150 g/10 minutes, the viscosity is low and the foamability is deteriorated, and there is a possibility that a molded article having uniform cells cannot be obtained.
  • a propylene-based polymer (A) having an MFR that satisfies the above range forms a uniform cell diameter, and can give a molded article with good appearance and excellent surface impact resistance.
  • the propylene/ethylene copolymer (a1) contained in the propylene-based polymer (A) according to the present invention usually contains 20 to 60 mol%, preferably 30 to 60 mol%, more preferably 30 to 60 mol% of structural units derived from ethylene. is in the range of 35 to 55 mol % [provided that the total amount of structural units derived from propylene and structural units derived from ethylene is 100 mol %. ].
  • the propylene/ethylene copolymer (a1) according to the present invention may contain biomass-derived monomers (propylene, ethylene). Monomers constituting the polymer may be only biomass-derived monomers, or may contain both biomass-derived monomers and fossil fuel-derived monomers. Biomass-derived monomers are monomers derived from any renewable natural sources and their residues, such as plant-derived or animal-derived, including fungi, yeasts, algae and bacteria, and containing 14C isotope as carbon. The biomass carbon concentration (pMC) measured according to ASTM D-6866 is about 100 (pMC). A biomass-derived monomer is obtained by a conventionally known method.
  • the propylene/ethylene copolymer (a1) according to the present invention contains a biomass-derived monomer from the viewpoint of environmental load reduction (mainly greenhouse gas reduction). If the polymer production conditions such as polymerization catalyst, polymerization process polymerization temperature, etc. are the same, even if the raw material monomer contains a biomass-derived monomer, it contains 14C isotope at a ratio of about 10 -12 to 10 -14 . has a molecular structure equivalent to that of a propylene-ethylene copolymer composed of fossil fuel-derived monomers. Therefore, the performance is assumed to be unchanged.
  • environmental load reduction mainly greenhouse gas reduction
  • the propylene/ethylene copolymer (a1) according to the present invention may contain chemically recycled monomers (propylene, ethylene).
  • the monomers constituting the polymer may be only chemically recycled monomers, or may include chemically recycled monomers and fossil fuel-derived monomers and/or biomass-derived monomers.
  • a chemically recycled monomer can be obtained by a conventionally known method.
  • the propylene/ethylene copolymer (a1) according to the present invention contains a monomer derived from chemical recycling from the viewpoint of reducing environmental load (mainly reducing waste).
  • the monomer derived from chemical recycling is a monomer obtained by depolymerizing or thermally decomposing a polymer such as waste plastic into a monomer unit such as ethylene, or using the monomer as a raw material. Since it is a produced monomer, its molecular structure is equivalent to that of a propylene/ethylene copolymer composed of fossil fuel-derived monomers, provided that polymer production conditions such as a polymerization catalyst, polymerization process, and polymerization temperature are the same. Therefore, the performance is assumed to be unchanged.
  • the MFR of the propylene homopolymer (a2) contained in the propylene-based polymer (A) according to the present invention is not particularly limited as long as the MFR of the propylene-based polymer (A) satisfies the above range.
  • MFR measured at a temperature of 230° C. and a load of 2.16 kg according to ASTM D-1238 is in the range of 50 to 1000 g/10 minutes, preferably 100 to 800 g/10 minutes, more preferably 200 to 800 g/10 minutes. .
  • the propylene homopolymer (a2) according to the present invention may contain biomass-derived propylene.
  • the propylene constituting the polymer may be only biomass-derived propylene, or may contain both biomass-derived propylene and fossil fuel-derived propylene.
  • Biomass-derived propylene is propylene sourced from any renewable natural raw material and its residues, such as plant-derived or animal-derived, including fungi, yeast, algae and bacteria, and has 14C isotope as carbon of 10 ⁇ 12 .
  • the biomass carbon concentration (pMC) measured according to ASTM D-6866 is about 100 (pMC).
  • Biomass-derived propylene is obtained by a conventionally known method.
  • the propylene homopolymer (a2) according to the present invention contains biomass-derived propylene from the viewpoint of environmental load reduction (mainly greenhouse gas reduction). If the polymer production conditions such as polymerization catalyst, polymerization process, polymerization temperature, etc. are the same, even if the raw material propylene contains biomass-derived propylene, it contains 14C isotope at a ratio of about 10 -12 to 10 -14 . Other molecular structures are equivalent to propylene homopolymers made from fossil fuel-derived propylene. Therefore, the performance is assumed to be unchanged.
  • the propylene homopolymer (a2) according to the present invention may contain propylene derived from chemical recycling.
  • the propylene constituting the polymer may be chemically recycled propylene only, or chemically recycled propylene and fossil fuel-derived propylene and/or biomass-derived propylene may be included.
  • Propylene derived from chemical recycling can be obtained by a conventionally known method.
  • the propylene homopolymer (a2) according to the present invention contains propylene derived from chemical recycling from the viewpoint of reducing environmental load (mainly reducing waste).
  • the monomer derived from chemical recycling is a monomer obtained by depolymerizing or thermally decomposing a polymer such as waste plastic into a monomer unit such as propylene, or using the monomer as a raw material. Since it is a produced monomer, its molecular structure is equivalent to that of a propylene homopolymer composed of a fossil fuel-derived monomer if polymer production conditions such as a polymerization catalyst, polymerization process and polymerization temperature are the same. Therefore, the performance is assumed to be unchanged.
  • the propylene-based polymer (A) according to the present invention can be produced by various known production methods, for example, by polymerizing the propylene homopolymer (a2) and the propylene/ethylene copolymer (a1) satisfying the above physical properties, followed by , a method of obtaining a propylene-based polymer (A) by mixing or melt-kneading a propylene homopolymer (a2) and a propylene/ethylene copolymer (a1), or a propylene homopolymer (a2 ) and the propylene/ethylene copolymer (a1) in one polymerization system or in two or more polymerization systems.
  • propylene-based polymer (A) according to the present invention is commercially available under the name of block copolymer produced by a known production method.
  • a copolymer (B) containing a unit derived from an alkenyl aromatic compound, which is one of the components contained in the propylene-based resin composition of the present invention [hereinafter sometimes referred to as "copolymer (B)" be. ] is a copolymer having an MFR measured at a temperature of 230° C. in accordance with ASTM D-1238 of 10 to 80 g/10 min, preferably 11 to 75 g/10 min, more preferably 12 to 73 g/10 min. It is a coalescence.
  • the copolymer (B) according to the present invention preferably has a density in the range of 0.88 to 0.98 g/cm 3 and is preferably an olefinic copolymer or a conjugated diene polymer with alkenyl It is produced by a method of bonding aromatic compounds by polymerization, reaction, or the like. Examples include block copolymers in which the double bond of the diene portion is hydrogenated.
  • the conjugated diene portion of a block copolymer comprising a vinyl aromatic compound polymer block and a conjugated diene polymer block
  • a block copolymer in which double bonds are hydrogenated more preferably a block copolymer in which 80% or more of the double bonds in the conjugated diene portion of the block copolymer are hydrogenated, more preferably It is a block copolymer in which 85% or more of the double bonds in the conjugated diene portion of the block copolymer are hydrogenated.
  • the copolymer (B) according to the present invention includes styrene-ethylene-butene-styrene rubber (SEBS), styrene-ethylene-propylene-styrene rubber (SEPS), and styrene-butadiene rubber.
  • SEBS styrene-ethylene-butene-styrene rubber
  • SEPS styrene-ethylene-propylene-styrene rubber
  • SBR styrene-butadiene rubber
  • SIS styrene-isoprene-styrene rubber
  • block copolymers obtained by hydrogenating these rubber components Among them, styrene-ethylene-butene-styrene rubber (SEBS) is preferably used because of its good compatibility with the propylene-based polymer (A).
  • SEBS styrene-ethylene-butene-styrene rubber
  • Examples of the method for producing the copolymer (B) according to the present invention include a method of bonding an alkenyl aromatic compound to an olefin copolymer or a conjugated diene rubber by polymerization, reaction, or the like.
  • copolymer (B) containing units derived from an alkenyl aromatic compound according to the present invention can be used alone or in combination of two or more different similar copolymers.
  • the ethylene-based copolymer (C) which is a component that may be contained in the propylene-based resin composition of the present invention, has an MFR of 20 to 40 g/10 minutes measured at a temperature of 230° C. according to ASTM D-1238. It is preferably an ethylene-based copolymer in the range of 21 to 38 g/10 min, more preferably 22 to 35 g/10 min.
  • the ethylene copolymer (C) according to the present invention preferably has a density of 0.85 to 0.98 g/cm 3 , more preferably 0.85 to 0.88 g/cm 3 , still more preferably 0.86 to 0.88 g/cm 3 . It is in the range of 0.87 g/cm 3 .
  • the ethylene-based copolymer (C) is a copolymer of ethylene and ⁇ -olefin, and generally includes linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), and high density polyethylene (HDPE).
  • LLDPE linear low density polyethylene
  • MDPE medium density polyethylene
  • HDPE high density polyethylene
  • the ⁇ -olefin to be copolymerized with ethylene is preferably an ⁇ -olefin having 3 to 20 carbon atoms, specifically propylene, 1-butene, 4-methyl-1-pentene-1 , 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1 -nonadecene, 1-eicosene, 9-methyl-1-decene, 11-methyl-1-dodecene and 12-ethyl-1-tetradecene.
  • 1-butene and 1-octene are particularly preferred. These ⁇ -olefins may be used alone or in combination of two or more.
  • the ethylene-based copolymer (C) according to the present invention can be used alone or in combination of two or more different ethylene-based copolymers.
  • the ethylene copolymer (C) according to the present invention can be produced by various known production methods.
  • the propylene-based resin composition of the present invention contains the propylene-based polymer (A) in an amount of 50 to 90% by mass, preferably 60 to 90% by mass, more preferably 70 to 80% by mass, and the alkenyl aromatic compound. 5 to 50% by mass, preferably 5 to 40% by mass, more preferably 5 to 30% by mass of the copolymer (B) containing the derived units, and the ethylene copolymer (C) is 0 to 20% by mass, preferably 1 to 20% by mass, more preferably 10 to 20% by mass [provided that the total amount of (A) + (B) + (C) is 100% by mass. ].
  • the propylene-based resin composition of the present invention contains the copolymer (B) in the above range in addition to the propylene-based polymer (A), so that it has a uniform cell diameter, a good appearance and a smooth surface. A molding having excellent impact resistance can be obtained.
  • the MFR of the propylene-based resin composition of the present invention measured at a temperature of 230°C according to ASTM D-1238 is preferably in the range of 40 to 120 g/10 minutes, more preferably 40 to 100 g/10 minutes. When the content is at least the lower limit, a molded article having a good appearance can be obtained.
  • the propylene-based resin composition of the present invention exhibits the same effect even if it contains an ethylene-based copolymer (C).
  • the propylene-based resin composition of the present invention may contain the following components in addition to the propylene-based polymer (A), the copolymer (B), and the ethylene-based copolymer (C).
  • the crystal nucleating agent is a nucleating agent that preferentially forms ⁇ -crystals of the propylene-based polymer (A). Nucleating agents, rosin metal salt-based nucleating agents, sorbitol-based nucleating agents, nonitol-based nucleating agents, xylitol-based nucleating agents, amide-based nucleating agents, and the like.
  • the propylene-based resin composition of the present invention contains the crystal nucleating agent (D), it is 0.5 per 100 parts by mass of the total amount of (A) + (B) + (C) in the propylene-based resin composition. Part by mass or less, preferably 0.4 part by mass or less.
  • the foaming agent to be mixed in the propylene-based resin composition of the present invention is not particularly limited, and any one that can be used for the intended foam molding may be selected and used.
  • foaming agent chemical foaming agents and physical foaming agents can be used.
  • Chemical blowing agents include decomposition-type blowing agents, and physical blowing agents include solvent-type blowing agents and gaseous blowing agents.
  • One type of foaming agent can be used alone, and two or more types of foaming agents can be used in combination.
  • decomposable foaming agents include the following compounds.
  • Inorganic blowing agents sodium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate, ammonium nitrite.
  • Organic blowing agents (a) N-nitroso compounds: N,N'-dinitrosoterephthalamide, N,N'-dinitrosopentamethylenetetramine.
  • Azo compounds azodicarbonamide, azobisisobutyronitrile, azocyclohexylnitrile, azodiaminobenzene, barium azodicarboxylate.
  • Sulfonylhydrazide compounds benzenesulfonylhydrazide, toluenesulfonylhydrazide, p,p'-oxybis(benzenesulfenylhydrazide), diphenylsulfone-3,3'-disulfonylhydrazide.
  • Azide compounds calcium azide, 4,4'-diphenyldisulfonyl azide, p-toluenesulfonyl azide.
  • the decomposition-type foaming agent may be used in combination with a foaming aid such as an organic acid such as citric acid or an organic acid metal salt such as sodium citrate, which induces the generation of gas by decomposition.
  • a foaming aid such as an organic acid such as citric acid or an organic acid metal salt such as sodium citrate, which induces the generation of gas by decomposition.
  • liquefied gases can be used as the solvent-type blowing agent.
  • specific examples include low-boiling aliphatic hydrocarbons such as propane, butane, neopentane, heptane, isohexane, hexane, isoheptane, and heptane, and freon gas. low boiling point fluorine-containing hydrocarbons.
  • Gaseous foaming agents include inert gases such as carbon dioxide, nitrogen, argon, helium, neon, and astatine. Gaseous blowing agents may be used in a supercritical state.
  • the blending ratio of the foaming agent is in the range of 0.1 to 10 parts by mass with respect to 100 parts by mass of the total amount of (A) + (B) + (C) in the propylene resin composition, and 0.1 to 10 parts by mass. It is preferably in the range of 5 parts by mass, more preferably in the range of 0.1 to 3.0 parts by mass.
  • the propylene-based resin composition of the present invention may optionally contain various additives within a range that does not impair its purpose.
  • additives include nucleating agents, antioxidants, hydrochloric acid absorbers, heat stabilizers, weather stabilizers, light stabilizers, ultraviolet absorbers, lubricants, antistatic agents, flame retardants, pigments, dyes, dispersants, Copper damage inhibitors, neutralizers, plasticizers, cross-linking agents, flow improvers such as peroxides, weld strength improvers, natural oils, synthetic oils, and waxes can be mentioned.
  • These 1 types can be used individually or in combination of 2 or more types.
  • the propylene-based resin composition of the present invention can be produced by various known production methods, for example, the propylene-based polymer (A), the copolymer (B), the ethylene-based copolymer (C), and, if necessary, , a crystal nucleating agent (D), a foaming agent (E), etc., in predetermined amounts, and mixed by a conventional method such as dry blending or melt-kneading in an extruder.
  • One form of the method for producing an injection foam molded article includes the steps of filling a mold for injection foam molding with a propylene-based resin composition, and foaming and solidifying the propylene-based resin composition in the mold, followed by injection. and obtaining a foam molded article.
  • the mold for injection foam molding, the method of filling the propylene-based resin composition into the mold for molding, and the conditions for foam molding may be selected according to the desired shape and physical properties of the foam molded product.
  • An injection foam molded product can be obtained by using an injection molding method in which the propylene-based resin composition is injected into the mold for molding.
  • the foaming agent may be mixed with components other than the foaming agent of the propylene-based resin composition and then introduced into the mold for molding. It may be injected and mixed into the resin material in the cylinder during injection molding or in the flow path from the cylinder to the cavity.
  • a core-back molding method can be suitably used for forming an injection foam molded article having a thin portion with a thickness of about 1.0 to 5.0 mm.
  • One form of mold used in the core-back molding method has a fixed mold and a movable mold. It is preferable that these molds are in a clamping state when the propylene-based resin composition is injected and filled. Further, the volume of the cavity in the mold to be injected and filled with the propylene-based resin composition can be increased by retracting (core-backing) the movable mold to widen the cavity.
  • the timing of activating the movable mold after completion of injection filling can be determined according to the desired expansion rate, foam shape, various physical properties of the injection foam molded product, and the like.
  • the moving speed of the movable mold during core backing can be selected according to conditions such as the thickness of the injection foam molded product, the composition of the propylene-based resin composition, the type and amount of foaming agent added, the mold temperature, and the resin temperature. can.
  • the temperature and mold temperature of the propylene-based resin composition to be injected can be selected according to the thickness of the molded body, the composition of the propylene-based resin composition, the type and amount of foaming agent added, and the like.
  • the temperature of the injected resin material can range from 170 to 250.degree. C., preferably from 180 to 220.degree.
  • the mold temperature of the fixed type and the movable type can be in the range of 10 to 100.degree. C., preferably 30 to 80.degree.
  • the injection pressure can be selected from the range of 10-250 MPa, preferably 12-200 MPa.
  • the temperature of the propylene-based resin composition injected into the mold is preferably higher than the mold temperature.
  • the injection foam molded article according to the present invention can be suitably used for various applications such as automotive interior and exterior parts, cardboard substitutes, electric appliances, and building materials.
  • Such an injection foam molded product can be particularly suitably used for automobile interior parts. It can be said that the automotive interior parts are suitable for door trims, rear side trims, luggage trims, roof trims, back door trims, deck side trims, and the like.
  • Propylene-based polymer (A) (1-1) Propylene-based polymer (A-1)
  • the propylene-based polymer (A) has an MFR of 75 g/10 minutes measured at a temperature of 230° C. according to ASTM D-1238, and a propylene/ethylene copolymer (a1-1) [room temperature n-decane soluble part].
  • Ethylene copolymer (C) (3-1) Ethylene-based copolymer (C-1)
  • ethylene-based copolymer (C) an ethylene/1-octene copolymer [ENGAGE (registered trademark) 8137] was used as the ethylene copolymer (C-1).
  • Propylene-based polymer (F) (4-1) Propylene-based polymer (F-1)
  • the propylene-based polymer (F) has an MFR of 66 g/10 min measured at a temperature of 230° C. according to ASTM D-1238, and a propylene/ethylene copolymer (f1-1) [room temperature n-decane soluble part].
  • Ethylene copolymer (G) 5-1) Ethylene-based copolymer (G-1) As the ethylene-based copolymer (G), an ethylene/1-octene copolymer [ENGAGE (registered trademark) 8407 manufactured by Dow Chemical Company] having a density of 0.87 g/cm 3 and an MFR of 60 g/10 min was used. , was used as the ethylene copolymer (G-1).
  • ENGAGE registered trademark
  • MFR 60 g/10 min
  • injection foam molding method The injection foam molded articles of the propylene-based resin compositions obtained in Examples and Comparative Examples were molded by the following method.
  • Injection molding machine Japan Steel Works, Ltd. J350ADS-460H (clamping force 350t) Mold: Cavity size: Length: 400mm, Width: 200mm, Thickness: 1.5mm Gate: Direct gate (installed in the center of the molded product) Injection cylinder set temperature: 200°C Mold surface temperature: 40°C Injection speed: 120mm/s Foam molding conditions: Mold clearance after completion of foaming process: 3.0 mm Core back time: 0.2s Foaming start delay time after composition filling: 0 s Mold cavity clearance during injection (L0): 1.5 mm The physical properties of injection foam molded articles were measured by the following methods.
  • ⁇ : Puncture energy value is 8.0 J or more.
  • the observation sample was observed with a microscope, binarized according to brightness, and the average perimeter of the cell was measured. A larger value indicates a coarser cell diameter.
  • the physical properties of the foam are superior when the cell diameter is small and uniform.
  • the cell size was determined as follows.
  • the average value of the cell circumference is less than 190 ⁇ m
  • a cell having an average cell circumference of 190 ⁇ m or more was regarded as defective.
  • the appearance of the injection foam molded product was visually observed, and the presence or absence of avatars and swirl marks was visually determined to evaluate the appearance. If both the avatar and the swirl mark were visually identifiable, they were evaluated as x, and if they were not visually identifiable, they were evaluated as ⁇ .
  • Example 1 76% by mass of the propylene polymer (A-1) and 24% by mass of the copolymer (B-1) were mixed and granulated to obtain a polypropylene resin composition for foam molding.
  • Example 2 Instead of the propylene-based polymer (A-1) used in Example 1, 74% by mass of the propylene-based polymer (A-2), 26% by mass of the copolymer (B-1), and crystal nuclei An injection foam molded article was obtained in the same manner as in Example 1 except that the amount of agent (D-1) was 0.2 parts by mass per 100 parts by mass of the total amount of (A) + (B).
  • Example 3 Instead of the polypropylene resin composition for foam molding used in Example 1, 76% by mass of the propylene polymer (A-1), 6% by mass of the copolymer (B-1), and an ethylene copolymer An injection foam molded article was obtained in the same manner as in Example 1, except that the coalescence (C-1) was 18% by mass.
  • Example 4 instead of the polypropylene resin composition for foam molding used in Example 1, the propylene polymer (A-1) was 76% by mass and the copolymer (B-2) was 24% by mass. An injection foam molded product was obtained in the same manner as in Example 1.
  • Example 1 instead of the polypropylene resin composition for foam molding used in Example 1, 76% by mass of the propylene polymer (A-1) and 24% by mass of the ethylene copolymer (G-1) are used. Except for this, the same procedure as in Example 1 was carried out to obtain an injection foam molded product.
  • Example 4 Example except that the polypropylene resin composition for foam molding used in Example 1 is replaced with 76% by mass of the propylene polymer (A-1) and 24% by mass of the copolymer (H-1) Injection foam molding was obtained in the same manner as in 1.
  • the injection foamed molded articles obtained in Examples 1 to 3 had a puncture energy value of 8.0 J or more, an average cell circumference of less than 190 ⁇ m, and good appearance. It is beautiful.
  • the injection foam molded article obtained in Comparative Example 1 does not contain the copolymer (B-1), so the puncture energy value is as low as 7.4 J, and the ethylene copolymer (G The cell diameter is coarse probably because the MFR of -1) is high.
  • the injection foam molded article obtained in Comparative Example 2 has a poor appearance due to an increase in the amount of gas generated due to shear heat generation, probably because the MFR of the propylene-based polymer is low and the fluidity is poor.
  • the injection foam molded article obtained in Comparative Example 3 has a low MFR of the propylene polymer and poor fluidity, and an increased amount of gas generation due to shear heat generation and poor appearance. Moreover, the cell diameter is coarse probably because the intrinsic viscosity [ ⁇ ] of the contained propylene/ethylene copolymer is low.
  • the injection foamed molded product obtained in Comparative Example 4 has a poor appearance due to an increase in the amount of gas generated due to shear heat generation, probably because the MFR of the resin is low and the fluidity is poor. Further, the copolymer (H-1) has an MFR of 7 g/10 min and a low puncture energy value of 7.9 J due to poor fluidity.

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0632951A (ja) * 1992-07-15 1994-02-08 Sumitomo Chem Co Ltd 熱可塑性樹脂組成物およびその射出成形体
JP2011079924A (ja) * 2009-10-06 2011-04-21 Japan Polypropylene Corp 自動車内装部品成形体
WO2012043824A1 (ja) * 2010-09-30 2012-04-05 東ソー株式会社 射出成形用樹脂組成物、射出発泡成形体および射出発泡成形体の製造方法
JP2014523460A (ja) * 2011-06-21 2014-09-11 ダウ グローバル テクノロジーズ エルエルシー ピペラジン系膨張性難燃剤を含むハロゲンフリー難燃性ポリマー組成物
JP2019031097A (ja) * 2014-10-30 2019-02-28 株式会社プライムポリマー ポリプロピレン系発泡成形体およびポリプロピレン系発泡成形体の製造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0632951A (ja) * 1992-07-15 1994-02-08 Sumitomo Chem Co Ltd 熱可塑性樹脂組成物およびその射出成形体
JP2011079924A (ja) * 2009-10-06 2011-04-21 Japan Polypropylene Corp 自動車内装部品成形体
WO2012043824A1 (ja) * 2010-09-30 2012-04-05 東ソー株式会社 射出成形用樹脂組成物、射出発泡成形体および射出発泡成形体の製造方法
JP2014523460A (ja) * 2011-06-21 2014-09-11 ダウ グローバル テクノロジーズ エルエルシー ピペラジン系膨張性難燃剤を含むハロゲンフリー難燃性ポリマー組成物
JP2019031097A (ja) * 2014-10-30 2019-02-28 株式会社プライムポリマー ポリプロピレン系発泡成形体およびポリプロピレン系発泡成形体の製造方法

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