WO2022153940A1 - プロピレン系樹脂組成物 - Google Patents

プロピレン系樹脂組成物 Download PDF

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Publication number
WO2022153940A1
WO2022153940A1 PCT/JP2022/000345 JP2022000345W WO2022153940A1 WO 2022153940 A1 WO2022153940 A1 WO 2022153940A1 JP 2022000345 W JP2022000345 W JP 2022000345W WO 2022153940 A1 WO2022153940 A1 WO 2022153940A1
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Prior art keywords
propylene
resin composition
based resin
polymer
copolymer
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PCT/JP2022/000345
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English (en)
French (fr)
Japanese (ja)
Inventor
若葉 浦野
悠 樋口
Original Assignee
住友化学株式会社
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Application filed by 住友化学株式会社 filed Critical 住友化学株式会社
Priority to CN202280009636.5A priority Critical patent/CN116670217A/zh
Priority to EP22739349.3A priority patent/EP4279541A4/en
Priority to US18/260,825 priority patent/US20240059882A1/en
Priority to JP2022575569A priority patent/JPWO2022153940A1/ja
Publication of WO2022153940A1 publication Critical patent/WO2022153940A1/ja

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    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/28—Nitrogen-containing compounds
    • C08K2003/287—Calcium, strontium or barium nitrates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3045—Sulfates
    • C08K2003/3063—Magnesium sulfate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/40—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Definitions

  • the present invention relates to a propylene-based resin composition.
  • the propylene-based resin composition containing the propylene-based polymer has good mechanical properties and is used for various purposes.
  • the molded product of the propylene-based resin composition can be particularly preferably used as an interior member of an instrument panel or a door trim automobile interior.
  • the interior of an automobile can be a closed space with a high temperature of, for example, 50 ° C. or higher, especially in summer. Therefore, the interior members of automobiles are required to be less likely to be deteriorated by heat, that is, to have high thermal stability.
  • an odor that causes discomfort to the driver, passengers, etc. may be generated from the interior member made of the molded body.
  • an odor that causes discomfort to the driver, passengers, etc. may be generated from the interior member made of the molded body.
  • zinc stearate is further added to a propylene-based resin composition containing talc as an inorganic filler (see Non-Patent Document 1).
  • Non-Patent Document 1 Although the generation of odor can be suppressed, the thermal stability cannot be said to be sufficient.
  • the present inventors have carried out diligent research in order to solve the above problems, and have completed the present invention.
  • the present invention provides the following [1] to [6].
  • [1] (A) Propylene-based polymer and (B) Inorganic filler and (C) A propylene-based resin composition containing a hindered amine-based light stabilizer.
  • a propylene obtained by molding the propylene-based resin composition under the following molding conditions X at 100 ° C. for 15 minutes and having a concentration of an amine compound in a volatile gas of 3 to 40 mass ppm. Based resin composition.
  • Molding conditions X molten resin temperature 200 ° C., mold temperature 40 ° C., filling pressure 15 MPa, holding pressure 4.3 MPa, holding pressure time 40 s, molded body take-out temperature ⁇ 60 ° C., total cycle time 60 s
  • the olefin-based polymer (D) is ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, ethylene-1-decene copolymer, ethylene- (3- (3-). Any of [1] to [3], which is at least one polymer selected from the group consisting of a methyl-1-butene) copolymer and a polymer of ethylene and an ⁇ -olefin having a cyclic structure.
  • the propylene-based resin composition according to item 1.
  • the content of (C) hindered amine-based light stabilizer is 0.3 parts by mass or less when the total amount of (A) propylene-based polymer and (B) inorganic filler is 100 parts by mass.
  • the propylene-based resin composition according to any one of [1] to [4].
  • Propylene resin composition [7] The propylene-based resin composition according to any one of [1] to [6], wherein the concentration of the amine compound in the volatile gas is 3 to 30 mass ppm.
  • a propylene-based resin composition capable of forming an interior member (molded body) having both high thermal stability and suppression of odor generation.
  • AA to BB means that it is AA or more and BB or less.
  • AA and BB represent numerical values, respectively, and AA ⁇ BB.
  • the unit of AA is the same as the unit described immediately after BB.
  • the term "monomer unit” means a structural unit having a structure obtained by polymerizing the monomer.
  • ⁇ -olefin means an olefin having a carbon-carbon double bond at the end.
  • the propylene-based resin composition according to the embodiment of the present invention is (A) Propylene polymer and (B) Inorganic filler and (C) A propylene-based resin composition containing a hindered amine-based light stabilizer.
  • concentration of the amine compound in the volatile gas generated when the molded product obtained by molding the propylene resin composition under the following molding condition X is heated at 100 ° C. for 15 minutes is 3 to 40 mass ppm.
  • Molding conditions X molten resin temperature 200 ° C., mold temperature 40 ° C., filling pressure 15 MPa, holding pressure 4.3 MPa, holding pressure time 40 s, molded body take-out temperature ⁇ 60 ° C., total cycle time 60 s
  • Molding conditions X molten resin temperature 200 ° C., mold temperature 40 ° C., filling pressure 15 MPa, holding pressure 4.3 MPa, holding pressure time 40 s, molded body take-out temperature ⁇ 60 ° C., total cycle time 60 s
  • a propylene-based polymer is a polymer containing more than 50% by mass of propylene units with respect to all the constituent units (100% by mass).
  • the propylene unit in the propylene-based polymer is usually 100% by mass or less.
  • Examples of the propylene-based polymer include a propylene homopolymer; and a copolymer of propylene and another monomer copolymerizable therewith.
  • the copolymer may be a random copolymer or a block copolymer.
  • Examples of other monomers copolymerizable with propylene include olefins other than propylene (eg, ethylene, olefins having 4 or more carbon atoms).
  • the olefin having 4 or more carbon atoms may be a linear olefin or a branched chain olefin.
  • the olefin having 4 or more carbon atoms may be an olefin having a cyclic structure, or may be an ⁇ -olefin having a cyclic structure such as vinylcyclopropane or vinylcyclobutane.
  • Non-propylene olefins that can be copolymerized with propylene are preferably ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, and 1-decene, and more.
  • Preferred are ethylene, propylene, 1-butene, 1-hexene, and 1-octene.
  • the propylene-based resin composition of the present embodiment may contain two or more kinds of the component (A) propylene-based polymer as the component (A) propylene-based polymer.
  • the propylene-based resin composition of the present embodiment may contain, as the component (A) propylene-based polymer, a propylene homopolymer (component (A-2)) in which only one kind of propylene monomer is polymerized, and two kinds thereof.
  • the above monomers may contain a propylene-based polymer polymerized in any combination of ratios.
  • component (A) propylene-based polymer examples include the component (A-2) propylene homopolymer and a random copolymer of propylene and another monomer copolymerizable therewith (hereinafter, propylene-based random co-polymer). Also referred to as a polymer).
  • Examples of combinations of propylene polymers in the case of containing two or more kinds of component (A) propylene-based polymers include combinations of two or more kinds of propylene homopolymers having different weight average molecular weights, the following polymers (I), and the following polymers (I). Examples thereof include a combination of the polymer (II).
  • the propylene-based resin composition of the present embodiment may contain the component (A-1) heterophasic propylene polymer material as the component (A) propylene-based polymer.
  • the component (A-1) heterophasic propylene polymer material contains two or more kinds of propylene-based polymers, and the two or more kinds of propylene-based polymers are not compatible with each other and are in different phases from each other. Means the material forming.
  • Examples of the component (A-1) heterophasic propylene polymer material include the following combinations of the polymer (I) and the polymer (II).
  • the polymer (I) is a polymer having a propylene unit of more than 80% by mass and 100% by mass or less with respect to the amount of all the constituent units.
  • the polymer (II) is a copolymer of a propylene unit and at least one monomer unit selected from the group consisting of an ethylene unit and an ⁇ -olefin unit having 4 or more carbon atoms.
  • the polymer (II) is preferably a polymer having propylene units in an amount of more than 0% by mass and 90% by mass or less, more preferably more than 0% by mass and 80% by mass or less, based on the amount of all the constituent units. Is.
  • the polymer (I) may be a propylene homopolymer or a copolymer of propylene and another monomer.
  • the polymer (I) and the polymer (II) may each consist of only one type of polymer or may contain two or more types of polymers.
  • the propylene-based polymer is one or more selected from the group consisting of propylene homopolymers and heterophasic propylene polymer materials from the viewpoint of improving the rigidity and impact resistance of the molded product obtained by molding the propylene-based resin composition. Is preferably included.
  • the propylene polymer is an isotactic pentad fraction (also referred to as [mmmm] fraction) measured by 13 C-NMR from the viewpoint of improving the rigidity of the molded product obtained by molding the propylene resin composition.
  • it is preferably 0.97 or more, and more preferably 0.98 or more.
  • the isotactic pentad fraction can be measured for the chain of propylene units in the copolymer.
  • the propylene-based polymer conforms to JIS K7210-1: 2014 and K7210-2: 2014 under the conditions of 230 ° C. and a load of 2.16 kgf from the viewpoint of improving the processability in molding of the propylene-based resin composition.
  • the melt flow rate (MFR) to be measured is preferably 1 g / 10 minutes or more, more preferably 3 g / 10 minutes or more, preferably 500 g / 10 minutes or less, and further preferably 3 g / 10 minutes. ⁇ 300 g / 10 minutes.
  • the propylene-based polymer can be produced, for example, by the following polymerization method using a polymerization catalyst.
  • Examples of the polymerization catalyst include a Cheegler-type catalyst system; a Cheegler-Natta-type catalyst system, a catalyst system containing a transition metal compound of Group 4 of the periodic table having a cyclopentadienyl ring, and an alkylaluminoxane, and a cyclopentadienyl ring.
  • Examples thereof include a catalyst system in which a transition metal compound, a compound forming an ionic complex, an organic aluminum compound, etc.) is supported on inorganic particles (eg, silica, clay mineral, etc.) and modified. Further, a prepolymerization catalyst prepared by prepolymerizing a monomer such as ethylene or ⁇ -olefin in the presence of such a catalyst system may be used. Examples of the Ziegler-Natta type catalyst system include a catalyst system in which a titanium-containing solid transition metal component and an organometallic component are used in combination.
  • Examples of such a catalyst system include JP-A-61-218606, JP-A-5-194685, JP-A-7-216017, JP-A-9-316147, and JP-A-10-212319. , The catalyst system described in JP-A-2004-182981.
  • the polymerization method examples include bulk polymerization, solution polymerization, and vapor phase polymerization.
  • the bulk polymerization refers to a method of carrying out polymerization using a liquid olefin as a medium at a polymerization temperature.
  • Solution polymerization refers to a method of polymerization in an inert hydrocarbon solvent such as propane, butane, isobutane, pentane, hexane, heptane, and octane.
  • Gas phase polymerization refers to a method of polymerizing a gaseous monomer in a medium using a gaseous monomer as a medium.
  • examples of the polymerization method include batch type, continuous type and combinations thereof.
  • the polymerization method may be a multi-stage method performed by using a plurality of polymerization reaction tanks connected in series.
  • the obtained propylene-based polymer is retained in order to remove the residual solvent contained in the obtained propylene-based polymer and the ultra-low molecular weight oligomer produced as a by-product during the production. It may be maintained at a temperature at which impurities such as the solvent and the oligomer can be volatilized and at a temperature lower than the temperature at which the propylene-based polymer melts.
  • Examples of the method for removing impurities such as the residual solvent and the oligomer include the methods described in JP-A-55-75410 and Japanese Patent No. 2565753.
  • the component (A-2) propylene homopolymer has an ultimate viscosity number [ ⁇ ] from the viewpoint of improving the fluidity of the propylene-based resin composition when melted and the toughness of the molded product obtained by molding the propylene-based resin composition. ], Is preferably 0.1 to 5 dL / g, more preferably 0.5 to 5 dL / g, and even more preferably 0.7 to 4 dL / g.
  • the ultimate viscosity number [ ⁇ ] is a numerical value measured at 135 ° C. using tetralin as a solvent.
  • the propylene homopolymer has a molecular weight distribution Mw / Mn preferably 2 or more and less than 10 from the viewpoint of improving the fluidity of the resin composition at the time of melting and the toughness of the molded product containing the resin composition. Yes, more preferably 3 to 8, and even more preferably 3 to 7.
  • Mw represents a weight average molecular weight
  • Mn represents a number average molecular weight.
  • the molecular weight distribution is a numerical value measured by gel permeation chromatography (also referred to as GPC).
  • a propylene-based random copolymer is a random copolymer containing a propylene unit and an ethylene unit (hereinafter, also referred to as a random polymer (1)); the propylene unit and ⁇ having 4 or more carbon atoms.
  • -Random copolymer containing olefin units hereinafter, also referred to as random polymer (2)
  • random polymer (3) examples thereof include a copolymer (hereinafter, also referred to as a random polymer (3)).
  • the ⁇ -olefin having 4 or more carbon atoms that can constitute a propylene-based random copolymer is preferably an ⁇ -olefin having 4 to 10 carbon atoms.
  • Examples of ⁇ -olefins having 4 to 10 carbon atoms include 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, and 1-decene, which are preferable. Are 1-butene, 1-hexene, and 1-octene.
  • Examples of the random copolymer (2) include a propylene-1-butene random copolymer, a propylene-1-hexene random copolymer, a propylene-1-octene random copolymer, and a propylene-1-decene random copolymer. Polymers can be mentioned.
  • random copolymer (3) examples include propylene-ethylene-1-butene copolymer, propylene-ethylene-1-hexene copolymer, propylene-ethylene-1-octene copolymer, and propylene-ethylene-.
  • 1-decene copolymer can be mentioned.
  • the content of ethylene units in the random copolymer (1) is preferably 0.1 to 40% by mass.
  • the content of the ⁇ -olefin unit having 4 or more carbon atoms in the random copolymer (2) is preferably 0.1 to 40% by mass, more preferably 0.1 to 30% by mass. More preferably, it is 2 to 15% by mass.
  • the total content of the ethylene unit and the ⁇ -olefin unit having 4 or more carbon atoms in the random copolymer (3) is preferably 0.1 to 40% by mass, more preferably 0.1 to 30% by mass. %, More preferably 2 to 15% by mass.
  • the content of the propylene unit in these random copolymers (1) to (3) is preferably 60 to 99.9% by mass, respectively.
  • the polymer (I) in the heterophasic propylene polymer material contains propylene units in an amount of more than 80% by mass and 100% by mass or less based on the amount of all the constituent units. It is a coalescence.
  • the total content of the monomer units other than the propylene unit in the polymer (I) is usually 0% by mass or more and less than 20% by mass when the mass of the polymer (I) is 100% by mass, and is 0% by mass. It may be 0.01% by mass or more.
  • Examples of the monomer unit other than the propylene unit that the polymer (I) may have include an ethylene unit and an ⁇ -olefin unit having 4 or more carbon atoms.
  • the ⁇ -olefin having 4 or more carbon atoms that can constitute the polymer (I) is preferably an ⁇ -olefin having 4 to 10 carbon atoms, and more preferably 1-butene or 1-hexene. And 1-octene, more preferably 1-butene.
  • Examples of the polymer (I) include a propylene homopolymer, a propylene-ethylene copolymer, a propylene-1-butene copolymer, a propylene-1-hexene copolymer, a propylene-1-octene copolymer, and a propylene.
  • Examples thereof include -ethylene-1-butene copolymer, propylene-ethylene-1-hexene copolymer, and propylene-ethylene-1-octene copolymer.
  • a propylene homopolymer a propylene-ethylene copolymer, a propylene-1-butene copolymer, and a propylene-ethylene-1-butene copolymer are preferable, and a propylene-based resin is used. From the viewpoint of the rigidity of the molded product obtained by molding the composition, a propylene homopolymer is more preferable.
  • the polymer (II) is a copolymer of a propylene unit and at least one monomer unit selected from the group consisting of an ethylene unit and an ⁇ -olefin unit having 4 or more carbon atoms. be.
  • the total content of the ethylene unit and the ⁇ -olefin unit having 4 or more carbon atoms in the polymer (II) is preferably 20 to 80% by mass when the mass of the polymer (II) is 100% by mass. %, More preferably 20 to 60% by mass.
  • the ⁇ -olefin having 4 or more carbon atoms that can form the polymer (II) is preferably an ⁇ -olefin having 4 to 10 carbon atoms and can form the polymer (I). Examples similar to those of ⁇ -olefins can be mentioned.
  • polymer (II) examples include propylene-ethylene copolymer, propylene-ethylene-1-butene copolymer, propylene-ethylene-1-hexene copolymer, propylene-ethylene-1-octene copolymer, and the like.
  • examples thereof include propylene-ethylene-1-decene copolymer, propylene-1-butene copolymer, propylene-1-hexene copolymer, propylene-1-octene copolymer, and propylene-1-decene copolymer. ..
  • the polymer (II) is preferably a propylene-ethylene copolymer, a propylene-1-butene copolymer, and a propylene-ethylene-1-butene copolymer, and more preferably a propylene-ethylene copolymer. Is.
  • the content of the polymer (II) in the component (A-1) heterophasic propylene polymer material is preferably 1 when the total mass of the polymer (I) and the polymer (II) is 100% by mass. It is ⁇ 50% by mass, more preferably 1 to 45% by mass, further preferably 5 to 40% by mass, and particularly preferably 8 to 32% by mass.
  • component (A-1) heterophasic propylene polymer material a combination of a propylene homopolymer and a (propylene-ethylene) copolymer in which the polymer (I) is a propylene homopolymer, propylene alone.
  • the heterophasic propylene polymer material may be a combination in which the polymer (I) is a polymer containing a propylene unit and a monomer unit other than the propylene unit.
  • the type of the polymer (I) is described first and the type of the polymer (II) is described later, specific examples of such a heterophasic propylene polymer material include a (propylene-ethylene) copolymer and a (propylene) copolymer.
  • the component (A-1) heterophasic propylene polymer material that can be contained in the propylene-based resin composition of the present embodiment includes a combination of a propylene homopolymer and a (propylene-ethylene) copolymer, and a propylene homopolymer.
  • the heterophasic propylene polymer material has a pre-stage polymerization step of producing the polymer (I) and a multi-stage polymerization step of producing the polymer (II) in the presence of the polymer (I) produced in the pre-stage.
  • the polymerization can be carried out using a catalyst system exemplified as a catalyst that can be used for producing the propylene-based polymer.
  • the ultimate viscosity number (hereinafter referred to as [ ⁇ ] I) of the polymer (I) (P part) is preferably 0.1 to 5 dL / g, more preferably 0.5 to 5 dL / g. Yes, more preferably 0.7-4 dL / g.
  • the ultimate viscosity number (hereinafter referred to as [ ⁇ ] II) of the polymer (II) (EP part) is preferably 1 to 10 dL / g, more preferably 2 to 10 dL / g, and further preferably. Is 2.5 to 8 dL / g.
  • the ratio of [ ⁇ ] II to [ ⁇ ] I ([ ⁇ ] II / [ ⁇ ] I) is preferably 0.5 to 20, more preferably 0.8 to 10, and even more preferably. It is 0.9-9.
  • the propylene-based polymer is a polymer material composed of the polymer (I) and the polymer (II) formed by multi-stage polymerization
  • the polymer formed by the previous stage polymerization is subjected to the polymerization in a polymerization tank.
  • the ultimate viscosity number of the polymer material finally obtained by multi-stage polymerization (hereinafter referred to as ([ ⁇ ] Total)) was obtained by extracting a part of the polymer material from the above.
  • the value and the content of each polymer may be used to calculate the ultimate viscosity number of the polymer formed by the subsequent polymerization.
  • a polymer material composed of the polymer (I) and the polymer (II) can be obtained by a method in which the polymer (I) is obtained in the first-stage polymerization step and the polymer (II) is obtained in the second-stage polymerization step.
  • the ultimate viscosity number ([ ⁇ ] I) of the polymer (I) obtained in the first-stage polymerization step, and the final polymer (that is, the polymer (I) and the polymer (II)) after the second-stage polymerization step From the ultimate viscosity number ([ ⁇ ] Total) measured by the above method of (coalescence) and the content of the polymer (II) contained in the final polymer, the ultimate viscosity number [ ⁇ ] II of the polymer (II) is determined. Calculate by the following formula.
  • [ ⁇ ] II ([ ⁇ ] Total- [ ⁇ ] I ⁇ XI) / XII [ ⁇ ] Total: Extreme viscosity number of final polymer (unit: dL / g) [ ⁇ ] I: Extreme viscosity number of polymer (I) (unit: dL / g) XI: Mass ratio of polymer (I) to final polymer XII: Mass ratio of polymer (II) to final polymer XI and XII are obtained from the mass balance at the time of polymerization.
  • the mass ratio XII of the polymer (II) to the final polymer may be calculated from the following formula using the amount of heat of crystal melting of each of the polymer (I) and the final polymer.
  • XII 1- ( ⁇ Hf) T / ( ⁇ Hf) P ( ⁇ Hf) T: Heat of fusion of the final polymer (polymer (I) and polymer (II)) (unit: cal / g) ( ⁇ Hf) P: Heat of fusion of polymer (I) (unit: cal / g)
  • the molecular weight distribution (Mw / Mn) of the polymer (I) measured by GPC is preferably 1 or more and less than 10, more preferably 2 or more and less than 7, and further preferably 3 or more and less than 5. ..
  • the content of the propylene-based polymer in the propylene-based resin composition of the present embodiment is preferably 30% by mass or more, more preferably 35% by mass, when the total amount of the propylene-based resin composition is 100% by mass. % Or more, more preferably 40% by mass or more, preferably 70% by mass or less, and preferably 30 to 70% by mass or less.
  • the propylene-based resin composition of the present embodiment may contain the component (B) inorganic filler.
  • the propylene-based resin composition may contain only one kind of inorganic filler, or may contain two or more kinds of inorganic fillers.
  • inorganic fillers include glass, silicate minerals (eg talc), silicon dioxide (eg silica), titanium oxide, iron oxide, aluminum oxide (eg alumina), magnesium oxide, antimony oxide, barium. Ferrite, strontium ferrite, beryllium oxide, magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, calcium carbonate, magnesium carbonate, carbonate minerals, calcium sulfate, magnesium sulfate, basic magnesium sulfate, calcium sulfite, and cadmium sulfide Can be mentioned.
  • the shape of the inorganic filler is not particularly limited.
  • the inorganic filler may have any shape such as a plate shape, a needle shape, and a fibrous shape.
  • the propylene-based resin composition contains talc, which is a plate-shaped silicate mineral, as an inorganic filler from the viewpoint of rigidity, impact resistance, and dimensional stability of the molded body obtained by molding the propylene-based resin composition. Is preferable.
  • talc for example, commercially available MWUPN-TT-H (manufactured by Hayashi Kasei Co., Ltd.) can be used.
  • the content of the inorganic filler in the propylene resin composition is preferably 0.01 to 50% by mass, more preferably 0.03 to 30%, when the total amount of the propylene resin composition is 100% by mass. It is mass%.
  • the content of talc in the propylene-based resin composition is preferably 0.01 to 50% by mass with respect to the propylene-based resin composition, and more. It is preferably 0.03 to 45% by mass, more preferably 1% by mass to 40% by mass, and particularly preferably 3% to 30% by mass.
  • the propylene-based resin composition of the present embodiment may contain a component (C) Hindered Amine-based light stabilizer.
  • the hindered amine-based light stabilizer that can be used has a function of capturing radicals generated by light (ultraviolet rays) in a propylene-based resin composition (molded product) and preventing deterioration due to decomposition of hydroperoxide.
  • the component (C) hindered amine light stabilizer may be either a low molecular weight hindered amine light stabilizer or a high molecular weight hindered amine light stabilizer.
  • hindered amine-based light stabilizers include (1) Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, (2) A mixture containing bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, (3) Bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,1-dimethylethyl) -4-hydrideiphenyl] methyl] butylmalonate, (4) Reaction product of bisdecanoic acid (2,2,6,6-tetramethyl-1 (octyloxy) -4-piperidyl) ester, 1,1-dimethylethylhydroperoxide and octane, (5) 4-Benzoyloxy-2,2,6,6-tetramethylpiperidine, (6) Ester mixture of 2,2,6,6-tetramethyl-4-piperidinol and
  • the hindered amine-based light stabilizer is a resin composition (molded product) having excellent photostability.
  • Component (C) As a hindered amine-based light stabilizer, component (C-1) bis (2,2,6,6-tetramethyl-4-piperidyl) sevacate represented by the following formula (eg, ADEKASTAB LA-77 (eg, ADEKASTAB LA-77) ADEKA)), component represented by the following formula (C-2) steric disorder amine oligomer "N- (2,2,6,6-tetramethyl-4-piperidyl) imide maleate and 20 to 20 carbon atoms Copolymer consisting of 24 ⁇ -olefins (eg, UVINUL (registered trademark) 5050H (manufactured by BASF Japan)), component (C-3) Butanedioc acid, dimethylester, polymer with 4-hydroxy-2,2,6 It is more preferable to use 6-polymerthyl-1-piperidine ethanol CAS. 65447-77-0 (eg, TINUVIN 622 SF (manufactured by
  • the content of the component (C) hindered amine-based light stabilizer in the propylene-based resin composition of the present embodiment is the content of the component (A) propylene-based polymer and the component (B) inorganic filler contained in the propylene-based resin composition.
  • the total amount is 100 parts by mass, it is preferably 1 part by mass or less, more preferably 0.5 part by mass or less, usually more than 0 part by mass, preferably 0.001 part by mass or more, and more. It is preferably 0.01 part by mass or more, and more preferably 0.03 part by mass or more.
  • the content of the hindered amine-based light stabilizer is set to the upper limit or less, the odor of the molded product obtained by molding the propylene-based resin composition can be effectively reduced, and the thermal stability can be effectively improved.
  • the propylene resin composition of the present embodiment may contain a component (D) olefin polymer.
  • the olefin-based polymer is, for example, an olefin copolymer containing an ethylene unit and an ⁇ -olefin unit having 4 or more carbon atoms.
  • an olefin copolymer containing an ethylene unit and an ⁇ -olefin unit having 4 or more carbon atoms is also referred to as an ethylene- ⁇ -olefin copolymer.
  • the propylene-based resin composition preferably contains an ethylene- ⁇ -olefin copolymer as the component (D) olefin-based polymer.
  • the propylene-based resin composition may contain only one type of ethylene- ⁇ -olefin copolymer, or may contain two or more types of ethylene- ⁇ -olefin copolymer.
  • the content of the ethylene- ⁇ -olefin copolymer in the propylene-based resin composition is preferably 0 to 40% by mass, more preferably 0 to 0 to 40% by mass, when the total amount of the propylene-based resin composition is 100% by mass. It is 30% by mass.
  • the content of the ethylene unit and the ⁇ -olefin unit having 4 or more carbon atoms in the ethylene- ⁇ -olefin copolymer is preferably 95% by mass with respect to the total mass of the ethylene- ⁇ -olefin copolymer. It is more preferably 98% by mass or more, further preferably 99% by mass or more, usually 100% by mass or less, and may be 100% by mass.
  • Examples of ⁇ -olefins having 4 or more carbon atoms that can constitute an ethylene- ⁇ -olefin copolymer include ⁇ -olefins having 4 to 12 carbon atoms (eg, 1-butene, 1-pentene, etc.). 1-hexene, 4-methyl-1-pentene, 1-octene and 1-decene).
  • the ⁇ -olefin having 4 or more carbon atoms that can constitute an ethylene- ⁇ -olefin copolymer is preferably 1-butene, 1-hexene, and 1-octene.
  • the ⁇ -olefin having 4 or more carbon atoms has a cyclic structure and may be an ⁇ -olefin having 4 or more carbon atoms (eg, vinylcyclopropane, vinylcyclobutane).
  • ethylene- ⁇ -olefin copolymer examples include ethylene-1-butene copolymer, ethylene-1-hexene copolymer, ethylene-1-octene copolymer, ethylene-1-decene copolymer, and ethylene- ( It is preferably at least one polymer selected from the group consisting of 3-methyl-1-butene) copolymers and copolymers of ethylene and ⁇ -olefin having a cyclic structure.
  • the ethylene- ⁇ -olefin copolymer it is more preferable to use the component (D-1) ethylene-1-butene copolymer.
  • the content of the ⁇ -olefin unit having 4 or more carbon atoms in the ethylene- ⁇ -olefin copolymer is preferably 1 to 49% by mass with respect to the total amount of the ethylene- ⁇ -olefin copolymer. It is more preferably 5 to 49% by mass, and even more preferably 24 to 49% by mass.
  • the ethylene- ⁇ -olefin copolymer preferably has a melt flow rate (MFR) measured in accordance with JIS K7210-1: 2014 and K7210-2: 2014 under the conditions of 190 ° C. and a load of 2.16 kgf. It is 0.1 g / 10 minutes to 80 g / 10 minutes.
  • MFR melt flow rate
  • the density of the ethylene- ⁇ -olefin copolymer is preferably 0.850 to 0.890 g / cm 3 from the viewpoint of enhancing the impact resistance of the molded product obtained by molding the propylene-based resin composition, preferably 0.850. It is more preferably ⁇ 0.880 g / cm 3 , and even more preferably 0.855 to 0.870 g / cm 3 .
  • the ethylene- ⁇ -olefin copolymer can be produced, for example, by polymerizing ethylene and an ⁇ -olefin having 4 or more carbon atoms using a polymerization catalyst.
  • a polymerization catalyst include the polymerization catalyst exemplified as the polymerization catalyst for producing the propylene-based polymer described above.
  • a commercially available product may be used as the component (D) ethylene- ⁇ -olefin copolymer.
  • Examples of such commercially available products are "Engage (registered trademark) 7447” manufactured by Dow Chemical Japan Co., Ltd., "Toughmer (registered trademark)” manufactured by Mitsui Chemicals Co., Ltd., and “Toughmer (registered trademark)” manufactured by Prime Polymer Co., Ltd., which are ethylene-butene-1 copolymers.
  • Neozex (registered trademark) and Ultozex (registered trademark) as well as Sumitomo Chemicals' Excellen FX (registered trademark), Sumikasen (registered trademark), and Esplen SPO (registered trademark). Be done.
  • the propylene-based resin composition of the present embodiment may contain a component (E) metal-based additive.
  • the component (E) metal-based additive is preferably at least one compound selected from the group consisting of a fatty acid zinc salt and a fatty acid aluminum salt.
  • the propylene-based resin composition of the present embodiment may contain only one type of fatty acid zinc salt as the component (E) metal-based additive, or may contain two or more types.
  • the propylene-based resin composition of the present embodiment may contain only one type of fatty acid aluminum salt as the component (E) metal-based additive, or may contain two or more types.
  • the fatty acid means a compound represented by R-COOH.
  • R represents a monovalent aliphatic hydrocarbon group.
  • the monovalent aliphatic hydrocarbon group represented by R may be linear or branched, and is preferably linear.
  • the monovalent aliphatic hydrocarbon group represented by R may have a carbon-carbon unsaturated bond, may not have a carbon-carbon unsaturated bond, and may have a carbon-carbon unsaturated bond. It is preferable not to have.
  • Examples of carbon-carbon unsaturated bonds that a monovalent aliphatic hydrocarbon group represented by R can have include carbon-carbon double bonds and carbon-carbon triple bonds, and carbon-carbon double bonds. Is preferable.
  • the carbon atom number of the fatty acid in the fatty acid salt which is the component (E) metal-based additive is preferably 10 or more, more preferably 11 or more, preferably 20 or less, and more preferably 18 or less.
  • the zinc fatty acid salt which is the component (E) metal-based additive may be a mono (fatty acid) zinc salt or a di (fatty acid) zinc salt.
  • the zinc fatty acid salt is preferably a di (fatty acid) zinc salt.
  • the aluminum fatty acid aluminum salt as the component (E) metal-based additive may be a mono (fatty acid) aluminum salt, a di (fatty acid) aluminum salt, or a tri (fatty acid) aluminum salt.
  • the fatty acid aluminum salt is a di (fatty acid) aluminum salt.
  • the propylene-based resin composition of the present embodiment may contain a fatty acid calcium salt as the component (E) metal-based additive.
  • the fatty acid calcium salt which is the component (E) metal-based additive may be a mono (fatty acid) calcium salt or a di (fatty acid) calcium salt.
  • the fatty acid calcium salt is preferably a di (fatty acid) calcium salt.
  • the fatty acid zinc salt which is the component (E) metal-based additive
  • lauric acid, stearic acid, palmitic acid, linoleic acid and the like are combined with zinc as monovalent fatty acids
  • oleic acid and linoleic acid and the like are combined with zinc as polyvalent fatty acids.
  • the fatty acid zinc is mentioned.
  • These fatty acids may contain saturated or unsaturated functional groups and / or cyclic structures, as well as hydroxy groups and the like.
  • fatty acid aluminum salt fatty acid aluminum in which lauric acid, stearic acid, palmitic acid, linoleic acid as monovalent fatty acids, oleic acid, linoleic acid and the like are combined with aluminum as polyvalent fatty acids is used.
  • fatty acids may contain saturated or unsaturated functional groups and / or cyclic structures, as well as hydroxy groups and the like.
  • Component (E) As an example of a fatty acid calcium salt which is a metal-based additive, lauric acid, stearic acid, palmitic acid, linoleic acid and the like are combined with calcium as monovalent fatty acids, and oleic acid and linoleic acid and the like are combined with calcium as polyvalent fatty acids.
  • Calcium fatty acid, and these fatty acids may contain a saturated or unsaturated functional group and / or a cyclic structure, a hydroxy group, and the like.
  • the propylene-based resin composition of the present embodiment may contain calcium hydroxide as the component (E) metal-based additive.
  • the propylene-based resin composition of the present embodiment contains two or more compounds as the component (E) metal-based additive, it preferably contains zinc distearate and aluminum distearate, and zinc distearate and It is more preferable to further contain calcium hydroxide in addition to aluminum distearate.
  • the content of the component (E) metal-based additive in the propylene-based resin composition is the propylene-based content contained in the propylene-based resin composition.
  • the total amount of the polymer and the inorganic filler is 100 parts by mass, it is usually 0 parts by mass or more, preferably 0.01 parts by mass or more, preferably 0.04 parts by mass or more, and more preferably. It is 0.1 part by mass or more, preferably 10 parts by mass or less, more preferably 3 parts by mass or less, further preferably 1 part by mass or less, and particularly preferably 0.6 part by mass or less.
  • the content of the metal-based additive is at least the lower limit value, the odor of the molded product obtained by molding the propylene-based resin composition can be effectively reduced, and the thermal stability can be effectively improved.
  • the propylene-based resin composition of the present embodiment may contain a component (F) lubricant.
  • a component (F) lubricant a conventionally known optional suitable lubricant can be used.
  • component (F) lubricant examples include ethylene bisstearic acid amide (eg, Alflo H-50S (manufactured by Nichiyu Co., Ltd.)), erucic acid amide, behenic acid amide, and oleic acid amide.
  • the content of the component (F) lubricant in the propylene-based resin composition is the propylene-based polymer contained in the propylene-based resin composition.
  • the total amount of the inorganic filler is 100 parts by mass, it is usually 0 parts by mass or more, preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and preferably 5 parts by mass. It is less than a part, more preferably 0.5 part by mass or less, still more preferably 0.1 part by mass.
  • the propylene-based resin composition of the present embodiment may contain a component (G) antioxidant.
  • a component (G) antioxidant a conventionally known arbitrary suitable antioxidant can be used.
  • component (G) antioxidant examples include phenolic antioxidants (eg, Sumilyzer GA80 (manufactured by Sumitomo Chemical Co., Ltd.)), sulfur-based antioxidants (eg, Smilizer TPM (manufactured by Sumitomo Chemical Co., Ltd.)) and phosphorus.
  • phenolic antioxidants eg, Sumilyzer GA80 (manufactured by Sumitomo Chemical Co., Ltd.)
  • sulfur-based antioxidants eg, Smilizer TPM (manufactured by Sumitomo Chemical Co., Ltd.)
  • phosphorus examples include system antioxidants (eg, SONGNOX6260 (manufactured by Songwon Co., Ltd.)).
  • the content of the component (G) antioxidant in the propylene-based resin composition is included in the propylene-based resin composition.
  • the total amount of the propylene-based polymer and the inorganic filler is 100 parts by mass, it is usually 0 parts by mass or more, preferably 0.01 parts by mass or more, and more preferably 0.03 parts by mass or more. It is preferably 1 part by mass or less, and more preferably 0.5 part by mass or less.
  • the propylene-based resin composition of the present embodiment may contain the component (H) ultraviolet absorber.
  • the component (H) ultraviolet absorber a conventionally known arbitrary suitable ultraviolet absorber can be used.
  • component (H) UV absorber examples include a benzoate-based UV absorber (eg, Sumisorb 400) and a phenol-based UV absorber (eg, Chemisove 114 (manufactured by Chemipro Kasei Co., Ltd.)).
  • a benzoate-based UV absorber eg, Sumisorb 400
  • a phenol-based UV absorber eg, Chemisove 114 (manufactured by Chemipro Kasei Co., Ltd.)
  • the content of the component (H) ultraviolet absorber in the propylene-based resin composition is included in the propylene-based resin composition.
  • the total amount of the propylene-based polymer and the inorganic filler is 100 parts by mass, it is usually 0 parts by mass or more, preferably 0.01 parts by mass or more, and more preferably 0.03 parts by mass or more. It is preferably 0.3 parts by mass or less, more preferably 0.2 parts by mass or less, and further preferably 0.1 parts by mass or less.
  • the propylene-based resin composition of the present embodiment may contain any suitable further optional component known conventionally, in addition to the components (A) to (H) already described.
  • optional components that can be contained in the propylene-based resin composition of the present embodiment include improvers, inorganic pigments, pigments such as organic pigments (eg, carbon black), pigment dispersants, neutralizers, weather resistant agents, and nucleating agents.
  • improvers inorganic pigments, pigments such as organic pigments (eg, carbon black), pigment dispersants, neutralizers, weather resistant agents, and nucleating agents.
  • Antistatic agent, anti-blocking agent, processing aid, organic peroxide, foaming agent, foam nucleating agent, plasticizer, flame retardant, cross-linking agent, cross-linking aid, high brightness agent, antibacterial agent, adsorbent examples thereof include a deodorant, a fluidity impact resistance improving agent by cross-linking, and a light diffusing agent.
  • the propylene-based resin composition may contain only one of the above optional components, or may contain two or more of the above optional components.
  • the propylene-based resin composition of the present embodiment is an amine compound in a volatile gas generated when a molded product obtained by injection-molding the propylene-based resin composition under the following molding condition X is heated at 100 ° C. for 15 minutes. Is contained, and the concentration thereof is 3 to 40 mass ppm. Molding conditions X: molten resin temperature 200 ° C., mold temperature 40 ° C., filling pressure 15 MPa, holding pressure 4.3 MPa, holding pressure time 40 s, molded body take-out temperature ⁇ 60 ° C., total cycle time 60 s
  • GC gas chromatograph mass spectrometry
  • Examples of the above amine compounds include propane-2-amine, tert-butylamine, 2-methylpropane-2-amine, tert-butyl (methyl) -l4-azane, 2-methylbutane-2-amine, N,2-.
  • a conventionally known arbitrary suitable device that is, a gas chromatograph mass spectrometer (GC-MS) device provided with a mass spectrometer (MS) device as a detector (eg, GC-2010 (manufactured by Shimadzu Corporation)).
  • GC-MS gas chromatograph mass spectrometer
  • MS mass spectrometer
  • the content of the amine compound is preferably 3 to 40 mass ppm, more preferably 3 to 30 mass ppm, still more preferably 5 to 30 mass ppm. It is mass ppm, more preferably 5 to 20 mass ppm, and most preferably 5 to 12 mass ppm.
  • the odor of the molded product obtained by molding the propylene-based resin composition is effectively reduced, and the thermal stability is also effective. Can be improved.
  • a propylene resin composition in which the concentration of the amine compound in the volatile gas generated when the molded product obtained by injection molding the propylene resin composition under the above conditions is heated at 100 ° C. for 15 minutes is 3 to 40 mass ppm.
  • a metal-based additive is described above in a propylene-based resin composition containing (A) a propylene-based polymer, (B) an inorganic filler, and (C) a hindered amine-based light stabilizer. It can be obtained by adding in an amount. Further, by adjusting the content of the (C) hindered amine-based light stabilizer, the concentration of the amine compound can be adjusted to 3 to 40 mass ppm.
  • the preferable content of the (C) hindered amine-based light stabilizer in the resin composition is as described above.
  • the propylene-based resin composition of the present embodiment has a melt flow rate (MFR) of propylene, which is measured in accordance with JIS K7210-1: 2014 and K7210-2: 2014 under the conditions of 230 ° C. and a load of 2.16 kgf. From the viewpoint of improving the processability in molding of the based resin composition, it is preferably 1 g / 10 minutes or more. It is more preferably 5 g / 10 minutes or more, further preferably 10 g / 10 minutes or more, and particularly preferably 15 g / 10 minutes or more.
  • the propylene resin composition of the present embodiment can be produced (prepared) by a conventionally known arbitrary suitable production method using the components already described.
  • the propylene-based resin composition of the present embodiment can be produced, for example, by melt-kneading the components that can be contained in the propylene-based resin composition.
  • the temperature of melt kneading can be, for example, 180 ° C. or higher, for example, 180 ° C. to 300 ° C., or 180 ° C. to 250 ° C.
  • Examples of the apparatus for producing the propylene-based resin composition of the present embodiment by melt-kneading include a Banbury mixer, a single-screw extruder, and a twin-screw extruder (eg, a twin-screw co-rotor extruder). Be done.
  • the order of addition of each component that can be contained in the propylene-based resin composition of the present embodiment is not particularly limited.
  • the produced propylene-based resin composition can have any conventionally known suitable shape and size, such as a strand shape, a sheet shape, a flat plate shape, and a pellet shape.
  • the propylene-based resin composition is preferably in the form of pellets having a length of 1 to 50 mm.
  • the method for producing a molded product containing the propylene-based resin composition of the present embodiment is not particularly limited.
  • a preferred example of the method for producing a molded product containing the propylene-based resin composition of the present embodiment is a conventionally known arbitrary suitable injection molding method.
  • Specific examples of the injection molding method include an injection foam molding method, a supercritical injection foam molding method, an ultrafast injection molding method, an injection compression molding method, a gas-assisted injection molding method, a sandwich molding method, a sandwich foam molding method, and an insert.
  • An outsert molding method can be mentioned.
  • the molded product containing the propylene-based resin composition of the present embodiment can be suitably used for material recycling applications.
  • the crushed product After crushing or crushing the molded product containing the propylene-based resin composition of the present embodiment, the crushed product can be melt-kneaded to produce a propylene-based resin composition.
  • the pulverized product When the pulverized product is melt-kneaded, the pulverized product may be mixed with another resin composition if necessary. If the propylene-based resin composition produced in this manner satisfies the above-mentioned conditions, it can be regarded as the propylene-based resin composition of the present embodiment.
  • the following methods can be mentioned as a method for producing a propylene-based resin composition when material is recycled.
  • a method for producing a propylene-based resin composition which comprises a step ( ⁇ ) and a step ( ⁇ ).
  • at least one selected from the group consisting of a propylene-based polymer, an inorganic filler, and a hindered amine-based light stabilizer may be melt-kneaded together with the pulverized product.
  • the propylene-based resin composition obtained is appropriately adjusted so as to satisfy the above conditions. Examples of the method for producing a molded product containing the olefin resin composition in the case of material recycling include the following methods.
  • a method for producing a molded product containing a propylene-based resin composition which comprises a step ( ⁇ ') and a step ( ⁇ ').
  • at least one selected from the group consisting of a propylene-based polymer, an inorganic filler, and a hindered amine-based light stabilizer may be mixed with a pulverized product for molding.
  • propylene-based resin composition and its molded product
  • the use of the propylene-based resin composition and its molded product of the present embodiment is not particularly limited.
  • the propylene-based resin composition can be suitably applied to various applications in which high thermal stability and reduction of odor are required.
  • the molded product produced by molding the propylene-based resin composition of the present embodiment can be suitably used as, for example, a member constituting an automobile, a member constituting a household electric appliance, and a container. Above all, it can be suitably used as a material for interior members for automobiles, which are required to have high thermal stability and suppression (reduction) of generation of odor. Specific examples of interior members for automobiles include door trims, pillars, and instrument panels.
  • thermogravimetric measuring device known in the past (eg, TG / DTA 6200 (Seiko Instruments Co., Ltd.). It can be evaluated using (manufactured by)).
  • a test piece obtained by molding the propylene resin composition of the present embodiment into a predetermined shape is used as a sample, and the oxidation induction time (unit: minutes) is measured at a set temperature of 190 ° C. and further at 210 ° C.
  • the time until the rise of the exothermic peak due to the oxidation of the test piece is defined as the oxidation induction time, and the thermal stability can be evaluated based on this.
  • the oxidation induction time (minutes) at the set temperature of 190 ° C. and the oxidation induction time (minutes) at the set temperature of 210 ° C. can be evaluated to be good if they are both 10 (minutes) or more. It is preferably 12 (minutes) or more, and more preferably 12 (minutes) or more.
  • the oxidation induction time (minutes) at the set temperature of 190 ° C. is more preferably 120 (minutes) or more.
  • the odor of a molded product obtained by molding a propylene resin composition can be evaluated by scoring by a plurality of panelists (testers) based on a predetermined scoring standard.
  • a test piece obtained by molding the propylene-based resin composition of the present embodiment into a predetermined shape is used as a sample, and the sample is placed in an odorless container (eg, a glass bottle) and sealed.
  • an odorless container eg, a glass bottle
  • the odor of the sample in the container For example, scoring is performed based on the following scoring criteria, the average score is calculated by dividing the total score obtained by totaling the scored points by the number of panelists, and the odor is objectively determined by the average score. Can be evaluated.
  • the above average score is preferably 3.2 points or less, more preferably 3.1 points or less, and most preferably 3.0 points or less.
  • the odor quality can also be evaluated.
  • the odor quality it is preferable that there is no unpleasant odor such as a burning odor, an amine odor, or an acrylic odor, and it is particularly preferable that there is no burning odor.
  • Component (A-1) Heterophasic propylene polymer material Liquid phase-gas phase weight using the polymerization catalyst obtained by the method described in Example 1 of JP-A-2004-182981.
  • the physical characteristics of the component (A-1) heterophasic propylene polymerized material are as follows. Melt flow rate (230 ° C, 2.16 kg load): 55 g / 10 minutes (a) Propylene homopolymer component (P part) Extreme viscosity number: 0.90 dL / g (b) Ethylene-propylene random copolymer component (EP part) Extreme viscosity number: 6.0 dL / g Content of structural units derived from ethylene: 32% by mass
  • Component (A-2) Propylene Homopolymer Using the polymerization catalyst obtained by the method described in Example 1 of JP-A-2004-182981 by the liquid phase-gas phase polymerization method, the component (A-2) propylene. A homopolymer was produced.
  • the physical characteristics of the component (A-2) propylene homopolymer are as follows. Melt flow rate (230 ° C, load 2.16 kgf): 3.2 g / 10 minutes Extreme viscosity number: 2.0 dL / g
  • the ultimate viscosity number (unit: dL / g) means a value measured at a temperature of 135 ° C. using tetralin as a solvent by the following method.
  • the reduced viscosity is measured for multiple concentrations using a Ubbelohde viscometer, the reduced viscosity is plotted against the concentration, and the concentration is extrapolated to zero. I asked for it.
  • Component (B) Inorganic filler Talc was used as the component (B) inorganic filler.
  • the physical characteristics are as follows. MWUPN-TT-H (manufactured by Hayashi Kasei Co., Ltd.) CAS No. 14807-96-6 Average particle size (50% particle size): 4.7 ⁇ m (measured using laser diffraction type SALD1100 (manufactured by Shimadzu Corporation))
  • Component (C-2) Steric hindrance amine oligomer "Copolymer consisting of N- (2,2,6,6-tetramethyl-4-piperidyl) maleate imide and ⁇ -olefin having 20 to 24 carbon atoms" CAS. 152261-33-1
  • component (C-2) a copolymer represented by the following formula was used. The physical characteristics are as follows.
  • UVINUL registered trademark
  • 5050H manufactured by BASF Japan Ltd.
  • Molecular weight 3500 pKa: 7.0
  • Weight loss rate by TG-DTA 2.2%
  • Component (D) Olefin Polymer A component (D-1) ethylene-butene-1 copolymer was used as the ethylene- ⁇ -olefin polymer which is a component (D) olefin polymer.
  • the physical characteristics of the component (D-1) ethylene-butene-1 copolymer are as follows. Engage (registered trademark) 7447 (manufactured by DOWN) Content of structural units derived from ethylene: 70% by mass Content of structural units derived from butene-1: 30% by mass Melt flow rate (190 ° C, load 2.16 kgf): 5 g / 10 minutes Density: 0.865 g / cm 3
  • Lubricants (1) Ethylene bisstearic acid amide Alflo H-50S (manufactured by NOF CORPORATION) CAS No. 324-27431
  • Ingredient (G) Antioxidant (1) Sumilyzer GA80 (manufactured by Sumitomo Chemical Co., Ltd.) CAS. 90498-90-1 (2) SONGNOX6260 (manufactured by Songwon) CAS. 26741-53-7 (3) Sumilyzer TPM (manufactured by Sumitomo Chemical Co., Ltd.) CAS. 16545-54-3 (4) IRGAFOS168 (manufactured by BASF) CAS. 31570-04-4
  • UV absorber Sumisorb 400 (manufactured by Sumika Chemtex) CAS. 4221-80-1
  • the molded product obtained by molding the propylene resin composition was evaluated as follows.
  • gas chromatograph GC-2010 manufactured by Shimadzu Corporation
  • Rix-5 as a column
  • helium gas was used as the carrier gas.
  • the cutting piece formed as described above was sealed in a sample bottle (volume 20 mL).
  • the sample bottle was heated at 100 ° C. for 15 minutes and the volatile components were injected into the GC inlet.
  • the temperature of the injection port was set to 250 ° C.
  • the column oven temperature was set to 40 ° C. and held for 10 minutes
  • the temperature was raised at 10 ° C./min
  • the temperature was further held at 290 ° C. for 10 minutes.
  • the flow rate was 1 mL / min and the split ratio was 50: 1.
  • MS mass spectrometer
  • EI electron impact ionization
  • the selective ion monitoring (SIM) method which can observe only a specific mass number (m / z), was used.
  • the "amine compound” was defined as a component containing N and NH as constituent components.
  • Quantification of amine compounds (unit: mass ppm) The quantification of the amine compound was performed by gas chromatography (GC) measurement according to the following procedure.
  • a gas chromatograph flash GC nose Heracles manufactured by Alpha Moss was used as an apparatus, Tenax TA (solid adsorbent trap) was used as a trap, and MXT-5 (filler: diphenyl dimethyl polysiloxane, length) was used as a column. 10 m, inner diameter 0.18 mm, thickness 0.14 ⁇ m) was used.
  • a hydrogen flame ionization detector (FID) was used as the detector, and hydrogen gas was used as the carrier gas.
  • the injection amount is 5000 ⁇ L
  • the injection port temperature is 220 ° C
  • the trap temperature is 70 ° C
  • the trap desorption temperature is 240 ° C
  • the column oven temperature is held at 40 ° C for 10 seconds, 1.5 ° C / sec.
  • the temperature was raised at 250 ° C. and held at 250 ° C. for 90 seconds.
  • the split ratio was 10: 1.
  • the FID detector temperature was 260 ° C.
  • the formed flat plate-shaped molded body was further molded by a vacuum press to a size suitable for measurement to form a test piece.
  • the vacuum press was carried out by setting the molding press temperature to 190 ° C., pressurizing at 0 MPa for 5 minutes and 1 MPa for 5 minutes, and then cooling at 25 ° C. and 0 MPa for 5 minutes. As a result, a test piece having a thickness of 300 ⁇ m was obtained.
  • the oxidation induction time was measured with the set temperature set to 190 ° C. and further to 210 ° C.
  • the atmospheric gas is quickly raised to the set temperature as nitrogen gas (N 2 )
  • the atmospheric gas is switched from nitrogen gas to air, and from the switching time to the rise of the exothermic peak due to the oxidation of the test piece.
  • the time was defined as the oxidation induction time (unit: minutes), and the thermal stability was evaluated based on this.
  • the maximum measurement time was 2 hours, and if no heat generation or weight loss was observed within the measurement time, the oxidation induction time was set to "120 minutes or more".
  • the propylene resin composition is supplied to an injection molding machine (“M70 type injection molding machine” manufactured by Meiki Seisakusho), and the molten resin temperature is 200 ° C., the mold temperature is 40 ° C., the filling pressure is 15 MPa, and the holding pressure is 4.3 MPa.
  • a flat molded body having a length of 60 mm, a width of 60 mm, and a thickness of 2.0 mm was formed with a holding pressure time of 40 s (seconds), a molded body take-out temperature of ⁇ 60 ° C., and a total cycle time of 60 s (seconds). Then, a cut piece obtained by cutting the obtained flat plate-shaped molded body into a size of 60 mm in length, 30 mm in width, and 2.0 mm in thickness was formed and used as a sample.
  • the three obtained samples were placed in an odorless glass bottle having a capacity of 0.5 L, the lid was closed and sealed, and the sample was heated in an oven at 80 ° C. for 2 hours.
  • the glass bottle was allowed to stand at 60 ° C. for 15 minutes. Next, three or more panelists evaluated the odor of the sample in the glass bottle.
  • each panelist scored the odor based on the following scoring criteria.
  • the average score was calculated by dividing the total score obtained by summing the scores scored by the panelists based on the above scoring criteria by the number of panelists, and evaluated by the average score. At the same time, the odor quality was also evaluated.
  • Example 1 When the total of the component (A) propylene-based polymer and the component (B) inorganic filler is 100 parts by mass, the component (A-1) propylene-ethylene block copolymer is 65 parts by mass and the component (A-2). ) 9 parts by mass of propylene homopolymer, 25.9 parts by mass of component (B) talc, 0.12 parts by mass of component (C) ADEKASTAB LA-77, which is a hindered amine-based light stabilizer, component (D) olefin-based weight.
  • component (D-1) ethylene-butene-1 copolymer
  • component (E) zinc stearate
  • calcium hydroxide 20.5 parts by mass of the coalescence (component (D-1) ethylene-butene-1 copolymer), 1.2 parts by mass of zinc stearate, which is a metal-based additive of component (E), and 0 parts of calcium hydroxide. .48 parts by mass, calcium stearate 0.024 parts by mass, component (F) lubricant ethylenebis stearate amide 0.084 parts by mass, component (G) antioxidant GA80 0.024 parts by mass , SONGNOX6260 by 0.06 parts by mass, Sumilyzer TPM by 0.024 parts by mass, and Sumisorb 400 by 0.06 parts by mass, and mixed so as to be uniform.
  • component (D-1) ethylene-butene-1 copolymer
  • zinc stearate which is a metal-based additive of component (E)
  • calcium hydroxide 20.5 parts by mass of the coalescence (
  • the cylinder temperature is 200 ° C.
  • the discharge rate is 50 kg / hour
  • the screw rotation speed is 200 rpm
  • the oxygen concentration of the feed hopper is 2%
  • the mixture is melt-kneaded and pelletized propylene.
  • a based resin composition was prepared.
  • the oxygen concentration in the feed hopper was measured by inserting the sensor of a portable oxygen concentration measuring device into the purge resin inlet attached to the feed hopper. Further, the condition of oxygen concentration of 2% was realized by circulating nitrogen gas to the feed hopper section.
  • the pellet-shaped propylene-based resin composition was dried at 100 ° C. for 1 hour, and then a molded product molded by an injection molding machine was formed as described above, and then the molded product was cut and further molded. Using the pieces, the amount of amine decomposition, odor, thermal stability and odor quality were evaluated by the methods already described. The results are shown in Table 3.
  • Example 2 to 6 The propylene-based resin compositions according to Examples 2 to 6 were prepared in the same manner as in Example 1 described above except that the blending amount of each component was as shown in Tables 1 and 2 below. It was evaluated in the same way. The results are shown in Table 3.

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