WO2024029197A1 - Composition de résine de polypropylène et corps moulé la contenant - Google Patents

Composition de résine de polypropylène et corps moulé la contenant Download PDF

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WO2024029197A1
WO2024029197A1 PCT/JP2023/021504 JP2023021504W WO2024029197A1 WO 2024029197 A1 WO2024029197 A1 WO 2024029197A1 JP 2023021504 W JP2023021504 W JP 2023021504W WO 2024029197 A1 WO2024029197 A1 WO 2024029197A1
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component
mass
polymer
polypropylene
resin composition
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PCT/JP2023/021504
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Japanese (ja)
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憧 栗本
健太 石塚
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住友化学株式会社
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/04—Monomers containing three or four carbon atoms
    • C08F10/06—Propene
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • 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
    • 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
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment

Definitions

  • the present invention relates to a polypropylene resin composition and a molded article containing the polypropylene resin composition.
  • Polypropylene resin has excellent moldability and is used as a material for automobile parts such as interior and exterior parts for automobiles.
  • a flame retardant synthetic resin composition containing a synthetic resin containing a polyolefin resin and a flame retardant containing a phosphate compound is known (Patent Document (See 1).
  • a polyolefin resin composition such as a polypropylene resin composition that can produce a molded article with excellent flame retardancy and has particularly good fluidity during the molding process.
  • the present inventors conducted extensive studies to solve the above problems, and found that the above problems could be solved by using a specific polypropylene resin composition, leading to the completion of the present invention.
  • the present invention provides the following [1] to [10].
  • Condition (a-2) The ratio of the component whose molecular weight (M) is 50,000 or less, calculated based on the molecular weight distribution curve obtained by GPC measurement, is 16 with respect to the total amount of the polypropylene polymer (A). % by mass or more.
  • the total amount of component (A) polypropylene polymer and component (B) flame retardant is 100 parts by mass
  • the content of component (A) polypropylene polymer is 30 to 95 parts by mass
  • component (D) an acid-modified polyolefin polymer.
  • Component (A) polypropylene polymer contains two or more types of polypropylene polymers, and at least one of the two or more types of polypropylene polymers satisfies the following conditions (a-3) and conditions ( The polypropylene resin composition according to [1] or [2], which satisfies a-4).
  • Condition (a-3) Melt flow rate (MFR) is 60 g/10 minutes or more.
  • the present invention it is possible to provide a polypropylene resin composition that has good fluidity in the molding process, and further a molded article with excellent flame retardancy obtained by molding the polypropylene resin composition.
  • AA to BB means AA or more and BB or less.
  • AA and BB each represent a numerical value, and AA ⁇ BB.
  • the unit of AA is the same as the unit written immediately after BB unless otherwise specified.
  • monomer unit means a structural unit (divalent group) produced when the monomer is polymerized.
  • ⁇ -olefin means an olefin having a carbon-carbon double bond at the end.
  • the intrinsic viscosity number (unit: dL/g) means a value measured at a temperature of 135° C. using tetralin as a solvent.
  • the limiting viscosity number is calculated by measuring the reduced viscosity at multiple concentrations using an Ubbelohde viscometer, plotting the reduced viscosity against the concentration, and extrapolating the concentration to zero.
  • the limiting viscosity number can be determined by the method. More specifically, using the method described in "Polymer Solution, Polymer Experimental Science 11" (Kyoritsu Shuppan Co., Ltd., 1982), page 491, concentrations of 0.1 g/dL, 0.2 g/dL and 0. It can be determined by measuring the reduced viscosity at three points of .5 g/dL, plotting the reduced viscosity against the concentration, and extrapolating the concentration to zero.
  • the polypropylene resin composition according to the present embodiment includes component (A) a polypropylene polymer and component (B) a flame retardant.
  • Component (A) is a polypropylene resin composition in which the polypropylene polymer satisfies the following conditions (A-1) and (A-2).
  • Condition (a-1) The ratio of the component whose molecular weight (M) is 2,000,000 or more, calculated based on the molecular weight distribution curve obtained by GPC measurement, is 0 with respect to the total amount of the polypropylene polymer (A). .6% by mass or more.
  • the polypropylene resin composition of this embodiment has good fluidity in the molding process, and furthermore, by using it, a molded article with excellent flame retardancy can be manufactured.
  • the polypropylene resin composition of this embodiment will be specifically explained.
  • Component (A) Polypropylene polymer is a polymer containing propylene units in an amount exceeding 50% by mass based on the total amount (total constituent units) of the polypropylene polymer. .
  • the propylene unit that can be contained in the component (A) polypropylene polymer is usually 100% by mass or less.
  • Examples of the polypropylene polymer include propylene homopolymers; and copolymers of propylene and other monomers that can be copolymerized with the propylene.
  • Such a copolymer may be a random copolymer or a block copolymer.
  • the polypropylene resin composition of the present embodiment may contain a single type of polypropylene polymer, or may contain a combination of two or more types of polypropylene polymers in any ratio.
  • the polypropylene polymer may be a fossil fuel-derived polypropylene polymer or a biomass-derived polypropylene polymer.
  • a recycled polypropylene polymer may be used as the polypropylene polymer.
  • Examples of one type of polypropylene polymer include a propylene homopolymer; and a random copolymer of propylene and another monomer that can be copolymerized with the propylene (hereinafter also referred to as a polypropylene random copolymer). ).
  • combinations of two or more polypropylene polymers include combinations of two or more propylene homopolymers with different weight average molecular weights, and furthermore, combinations of polymers (I) and polymers (II) described below. Can be mentioned.
  • the polypropylene resin composition of the present embodiment may contain a heterophasic propylene polymer material as the polypropylene polymer.
  • the heterophasic propylene polymer material includes two or more types of polypropylene polymers, and the two or more types of polypropylene polymers are contained in a state in which they are not compatible and form different phases. It means the material that is used.
  • heterophasic propylene polymer materials include materials containing a combination of polymer (I) and polymer (II).
  • the polymer (I) is a polymer having propylene units in an amount of more than 80% by mass and 100% by mass or less based on the amount of all structural units, and the polymer (II) is a polymer having propylene units and ethylene units. and at least one monomer unit selected from the group consisting of ⁇ -olefin units having 4 or more carbon atoms.
  • the polymer (I) may be a propylene homopolymer or a copolymer of propylene and other monomers.
  • the polymer (I) and the polymer (II) may each be a single type of polymer, or may contain two or more types of polymers.
  • Component (A) polypropylene polymer preferably consists of a propylene homopolymer and a heterophasic propylene polymer material from the viewpoint of improving the rigidity and impact resistance of a molded article formed from the polypropylene resin composition.
  • Component (A) polypropylene polymer has an isotactic pentad fraction ([mmmm] fraction measured by 13 C-NMR) from the viewpoint of improving the rigidity of a molded article made of a polypropylene resin composition. ) is preferably 0.97 or more, more preferably 0.98 or more.
  • the isotactic pentad fraction of the component (A) polypropylene polymer is to 1, the higher the stereoregularity of the molecular structure of the polypropylene polymer, and the higher the crystallinity of the polypropylene polymer.
  • the component (A) polypropylene polymer is a copolymer
  • the isotactic pentad fraction of the chain of propylene units in the copolymer can be measured.
  • Component (A) polypropylene polymer is compliant with JIS K7210-1:2014 and K7210-2:2014 at 230°C and under a load of 2.16 kgf from the viewpoint of improving processability in the molding process of polypropylene resin compositions.
  • the polypropylene polymer (Component (A)) can be produced, for example, by the polymerization method described below using the polymerization catalyst described below.
  • polymerization catalysts examples include Ziegler catalyst; Ziegler-Natta catalyst; catalyst containing a transition metal compound of Group 4 of the periodic table having a cyclopentadienyl ring and an alkylaluminoxane; A catalyst containing a transition metal compound of Group 4 of the periodic table, a compound that reacts with it to form an ionic complex, and an organoaluminum compound; Examples include catalysts in which complex-forming compounds, organic aluminum compounds, etc.) are supported on inorganic particles (silica, clay minerals, etc.) and modified. Further, a prepolymerized catalyst prepared by prepolymerizing monomers such as ethylene and ⁇ -olefin in the presence of the above catalyst may be used. Examples of Ziegler-Natta catalysts include catalysts in which a titanium-containing solid transition metal component and an organometallic component are combined.
  • polymerization catalyst examples include JP-A-61-218606, JP-A-5-194685, JP-A-7-216017, JP-A-9-316147, JP-A-10-212319, and Examples include the catalyst described in JP-A No. 2004-182981.
  • Examples of polymerization methods include bulk polymerization, solution polymerization, and gas phase polymerization.
  • bulk polymerization refers to a method in which polymerization is carried out using a liquid olefin as a medium at a polymerization temperature.
  • Solution polymerization refers to a method in which polymerization is carried out in an inert hydrocarbon solvent such as propane, butane, isobutane, pentane, hexane, heptane, octane, or the like.
  • Gas phase polymerization refers to a method in which a gaseous monomer is used as a medium and the gaseous monomer is polymerized in the medium.
  • Examples of the polymerization method in the polymerization method include a batch method, a continuous method, and a combination thereof.
  • the polymerization method may be a multistage method using a plurality of polymerization reactors connected in series.
  • Conditions in the polymerization step may be appropriately determined in consideration of the structure, properties, etc. of the target component (A) polypropylene polymer.
  • component (A) polypropylene polymer In the production of component (A) polypropylene polymer, residual solvent contained in the obtained polypropylene polymer, ultra-low molecular weight oligomers produced as by-products during production, etc. are removed in order to remove the obtained polypropylene polymer. may be maintained at a temperature at which impurities such as residual solvents and oligomers can volatilize and which is lower than the temperature at which the polypropylene polymer melts.
  • Specific examples of methods for removing impurities such as residual solvents and oligomers include methods described in JP-A-55-75410 and Japanese Patent No. 2,565,753.
  • the propylene homopolymer has an intrinsic viscosity [ ⁇ ] of is preferably 0.1 to 3 dL/g, more preferably 0.5 to 3 dL/g, and still more preferably 0.7 to 2.5 dL/g.
  • the propylene homopolymer preferably has a molecular weight distribution Mw/Mn of 3 from the viewpoint of improving the melting fluidity of the propylene resin composition and the toughness of a molded article obtained by molding the propylene resin composition.
  • the number is less than 15, more preferably 3 to 12.
  • Mw represents the weight average molecular weight
  • Mn represents the number average molecular weight.
  • the molecular weight distribution in this embodiment can be calculated according to a conventional method based on gel permeation chromatography (sometimes referred to as GPC) measurement.
  • polypropylene random copolymer examples include random copolymers containing propylene units and ethylene units (also referred to as random copolymers (1)); propylene units and ⁇ -olefin units having 4 or more carbon atoms; a random copolymer (also referred to as random copolymer (2)); and a random copolymer (also referred to as random copolymer (Also referred to as union (3)).
  • the ⁇ -olefin having 4 or more carbon atoms that can constitute the polypropylene 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.
  • the ⁇ -olefin having 4 or more carbon atoms is preferably 1-butene, 1-hexene, and 1-octene.
  • Examples of the random copolymer (2) include propylene-1-butene random copolymer, propylene-1-hexene random copolymer, propylene-1-octene random copolymer, and propylene-1-decene random copolymer. Examples include polymers.
  • random copolymer (3) examples include propylene-ethylene-1-butene copolymer, propylene-ethylene-1-hexene copolymer, propylene-ethylene-1-octene copolymer, and propylene-ethylene-1-octene copolymer.
  • Examples include 1-decene copolymers.
  • the content of ethylene units in the random copolymer (1) is preferably 0.1 to 40% by mass, more preferably 0.1 to 30% by mass, and even more preferably 2 to 15% by mass. be.
  • the content of ⁇ -olefin units 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 2 to 15% by mass.
  • the total content of ethylene units and ⁇ -olefin units 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. % by mass, more preferably 2 to 15% by mass.
  • the content of propylene units in the random copolymers (1), (2) and (3) is preferably 60 to 99.9% by mass, more preferably 70 to 99.9% by mass, More preferably, it is 85 to 98% by mass.
  • the polymer (I) is a polymer having propylene units in an amount of more than 80% by mass and not more than 100% by mass based on the amount of all structural units.
  • the total content of monomer units other than propylene units in the polymer (I) is usually 0% by mass or more and less than 20% by mass, and 0% by mass when the weight of the polymer (I) is 100% by mass. %, or 0.01% by mass or more.
  • Examples of monomer units other than propylene units that the polymer (I) may have include ethylene units and ⁇ -olefin units 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, more preferably 1-butene, 1-hexene, and 1-butene. -octene, more preferably 1-butene.
  • Examples of the polymer (I) include propylene homopolymer, propylene-ethylene copolymer, propylene-1-butene copolymer, propylene-1-hexene copolymer, propylene-1-octene copolymer, propylene -ethylene-1-butene copolymer, propylene-ethylene-1-hexene copolymer, and propylene-ethylene-1-octene copolymer.
  • propylene homopolymer propylene-ethylene copolymer, propylene-1-butene copolymer, and propylene-ethylene-1-butene copolymer are preferable, and the resin composition A propylene homopolymer is more preferable from the viewpoint of the rigidity of a molded article containing.
  • the polymer (II) is a copolymer of propylene units and at least one monomer unit selected from the group consisting of ethylene units and ⁇ -olefin units having 4 or more carbon atoms. .
  • the total content of ethylene units and ⁇ -olefin units having 4 or more carbon atoms in the polymer (II) is preferably 20 to 20% when the weight of the polymer (II) is 100% by mass. It is 80% by mass, more preferably 20 to 60% by mass.
  • the ⁇ -olefin having 4 or more carbon atoms that can constitute the polymer (II) is preferably an ⁇ -olefin having 4 to 10 carbon atoms, and can constitute the polymer (I). Examples similar to those of ⁇ -olefins that can be cited are given.
  • Examples of the polymer (II) include propylene-ethylene copolymer, propylene-ethylene-1-butene copolymer, propylene-ethylene-1-hexene copolymer, propylene-ethylene-1-octene copolymer, Examples 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, more preferably a propylene-ethylene copolymer. .
  • the content of polymer (II) in the heterophasic propylene polymer material is preferably 1 to 50% by mass when the total weight of polymer (I) and polymer (II) is 100% by mass. , more preferably 1 to 40% by weight, still more preferably 5 to 30% by weight, particularly preferably 8 to 15% by weight.
  • heterophasic propylene polymer materials include a combination of polymer (I) with propylene homopolymer and polymer (II). That is, such combinations include, for example, a combination of a propylene homopolymer and a (propylene-ethylene) copolymer; a combination of a propylene homopolymer and a (propylene-ethylene-1-butene) copolymer; Combination of polymerization and (propylene-ethylene-1-hexene) copolymer; combination of propylene homopolymer and (propylene-ethylene-1-octene) copolymer; combination of propylene homopolymer and (propylene-1-butene) copolymer; ) combination with copolymer; combination with propylene homopolymer and (propylene-1-hexene) copolymer; combination with propylene homopolymer and (propylene-1-octene) copolymer; and propylene homopolymer
  • heterophasic propylene polymer material includes the following combination of polymers, in which the polymer (I) is a polymer containing propylene units and monomer units other than propylene units.
  • the type of polymer (I) will be described first, and the type of polymer (II) will be described later.
  • such combinations include, for example, a combination of a (propylene-ethylene) copolymer and a (propylene-ethylene) copolymer; a combination of a (propylene-ethylene) copolymer and a (propylene-ethylene-1-butene) copolymer; Combination with coalescence; Combination with (propylene-ethylene) copolymer and (propylene-ethylene-1-hexene) copolymer; (Propylene-ethylene) copolymer and (propylene-ethylene-1-octene) copolymer Combination with coalescence; combination with (propylene-ethylene) copolymer and (propylene-ethylene-1-decene) copolymer; combination with (propylene-ethylene) copolymer and (propylene-1-butene) copolymer Combination of (propylene-ethylene) copolymer and (propylene-1-hexene) copolymer; Combination of (propylene-ethylene)
  • the heterophasic propylene polymer material that can be included in the propylene-based resin composition is preferably (a combination of a propylene homopolymer and a (propylene-ethylene) copolymer, a combination of a propylene homopolymer and a (propylene-ethylene) copolymer, a combination of a propylene homopolymer and a (propylene-ethylene-1- (butene) copolymer, (propylene-ethylene) copolymer and (propylene-ethylene) copolymer, (propylene-ethylene) copolymer and (propylene-ethylene-1-butene) copolymer A combination with a (propylene-1-butene) copolymer and a (propylene-1-butene) copolymer, and more preferably a propylene homopolymer and a (propylene-ethylene) copolymer. It is a combination of
  • the heterophasic propylene polymer material consists of a first stage polymerization step in which polymer (I) is produced and a second stage stage in which polymer (II) is further produced in the presence of polymer (I) produced in the first stage polymerization step. It can be produced by multi-stage polymerization including polymerization steps. These polymerization steps can be carried out using the catalysts exemplified as catalysts that can be used in the production of the polypropylene polymers described above.
  • the molecular weight distribution (Mw/Mn) of the polymer (I) calculated based on GPC measurement is preferably 3 or more and less than 15, more preferably 3 to 12.
  • the content of the polypropylene polymer (A) in the polypropylene resin composition is preferably 30% by mass or more, more preferably 35% by mass when the total amount of the polypropylene resin composition is 100% by mass. or more, more preferably 40% by mass or more, preferably 70% by mass or less, more preferably 65% by mass or less, even more preferably 60% by mass or less, and preferably 30 to 70% by mass. It is.
  • the component (A) polypropylene polymer is the component (A )
  • the ratio of the component having a molecular weight (M) of 2,000,000 or more, calculated based on the molecular weight distribution curve obtained by GPC measurement, is preferably 0.5% by mass or more with respect to the total amount of the polypropylene polymer. , more preferably 0.6% by mass or more, still more preferably 0.9% by mass or more, preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 2.5% by mass. % by mass or less, preferably in the range of 0.6 to 3.0% by mass, more preferably in the range of 0.6 to 2.5% by mass.
  • the component (A) polypropylene polymer is the component (A )
  • the ratio of components having a molecular weight (M) of 50,000 or less, calculated based on the molecular weight distribution curve obtained by GPC measurement, relative to the total amount of the polypropylene polymer is preferably 16% by mass or more, and more Preferably 20% by mass or more, preferably 40% by mass or less, more preferably 35% by mass or less, even more preferably 28% by mass or less, preferably in the range of 16 to 35% by mass, More preferably, it is in the range of 20 to 35% by mass.
  • the component (A) polypropylene polymer is the component (A )
  • the ratio of components whose molecular weight (M) is greater than 50,000 and less than 2,000,000, calculated based on the molecular weight distribution curve obtained by GPC measurement, with respect to the total amount of the polypropylene polymer is preferably 50 to 84. It is in the range of .5% by weight, more preferably in the range of 60 to 79.5% by weight, even more preferably in the range of 60 to 76.0% by weight.
  • the ratio of components whose molecular weight (M) is 2,000,000 or more and the ratio of components whose molecular weight (M) is 50,000 or less can be calculated based on the integral value of the molecular weight distribution curve obtained by GPC measurement. can.
  • the component (A) polypropylene polymer preferably satisfies the following conditions (a-1) and (a-2).
  • Condition (a-1) The ratio of the component whose molecular weight (M) is 2,000,000 or more, calculated based on the molecular weight distribution curve obtained by GPC measurement, is 0 with respect to the total amount of the polypropylene polymer (A). .6% by mass or more.
  • Condition (a-2) The ratio of the component whose molecular weight (M) is 50,000 or less, calculated based on the molecular weight distribution curve obtained by GPC measurement, is 16 with respect to the total amount of the polypropylene polymer (A). % by mass or more.
  • the polypropylene resin composition of the present embodiment by setting the ratio of the component having a molecular weight (M) of 2,000,000 or more to the component having a molecular weight (M) of 50,000 or less as described above, fluidity in the molding process is improved. In addition, it is possible to improve the flame retardancy of the molded article, and it is possible to achieve a good balance between fluidity and flame retardancy.
  • the component (A) polypropylene polymer may contain two or more types of polypropylene polymers.
  • the polypropylene resin composition of the present embodiment contains two or more types of polypropylene polymers
  • at least one of the two or more types of polypropylene polymers is satisfied under the following conditions (a-3).
  • condition (a-4) are preferably satisfied.
  • melt flow rate (MFR) is 60 g/10 minutes or more.
  • the melt flow rate is preferably 80 g/10 minutes or more, more preferably 90 g/10 minutes or more, from the viewpoint of improving the fluidity of the polypropylene resin composition in the molding process. , preferably 1000 g/10 minutes or less, more preferably 500 g/10 minutes or less.
  • Condition (a-4) When the total amount of component (A) polypropylene polymer is 100% by mass, the content of at least one of the two or more polypropylene polymers is 1 to 99% by mass. be. In condition (a-4), the content is preferably 30 to 90% by mass, more preferably 55 to 90% by mass from the viewpoint of improving the fluidity of the polypropylene resin composition in the molding process. .
  • the component (A) polypropylene polymer preferably satisfies the following condition (a-5) from the viewpoint of improving fluidity and flame retardancy.
  • the polypropylene resin composition of this embodiment contains component (B) a flame retardant.
  • the polypropylene resin composition of the present embodiment may contain one type of component (B) flame retardant alone, or may contain two or more types of flame retardants in any combination or in any ratio. good.
  • component (B) flame retardant examples include halogen-based flame retardants, guanidine-based flame retardants, phosphorus-containing flame retardants, metal oxides, and polyvalent hydroxyl group-containing compounds.
  • component (B) flame retardant it is preferable to use a phosphorus-containing flame retardant from the viewpoint of improving flame retardancy and further reducing environmental load.
  • halogenated flame retardants include organic halogenated aromatic compounds.
  • organic halogenated aromatic compounds include halogenated diphenyl compounds, halogenated bisphenol compounds, halogenated bisphenol bis(alkyl ether) compounds, and halogenated phthalimide compounds.
  • halogenated diphenyl compounds include halogenated diphenyl ether compounds, halogenated diphenyl ketone compounds, and halogenated diphenyl alkane compounds.
  • halogenated bisphenol compounds include halogenated bisphenyl alkane compounds, halogenated bisphenyl ether compounds, halogenated bisphenylthioether compounds, and halogenated bisphenyl sulfone compounds.
  • halogenated bisphenol bis(alkyl ether) compounds include brominated bisphenol A (brominated aliphatic ether), brominated bisphenol S (brominated aliphatic ether), chlorinated bisphenol A (chlorinated aliphatic ether), and chlorinated bisphenol S (chlorinated aliphatic ether).
  • Specific examples of halogenated bisphenol bis(alkyl ether) compounds include etherified tetrabromobisphenol A and etherified tetrabromobisphenol S.
  • guanidine-based flame retardants examples include guanidine compounds such as guanidine nitride.
  • a phosphorus-containing flame retardant is a flame retardant that contains a phosphorus atom.
  • the polypropylene resin composition of this embodiment preferably contains a phosphorus-containing flame retardant.
  • the polypropylene resin composition of the present embodiment may contain one type of phosphorus-containing flame retardant alone, or may contain a combination of two or more types of phosphorus-containing flame retardants in any proportion.
  • Examples of phosphorus-containing flame retardants include phosphates, polyphosphates, and phosphoric esters.
  • phosphates include melamine orthophosphate, piperazine orthophosphate, melamine pyrophosphate, piperazine pyrophosphate, calcium phosphate, and magnesium phosphate.
  • polyphosphates include ammonium polyphosphate, piperazine polyphosphate, and melamine polyphosphate.
  • phosphates and polyphosphates include salts of orthophosphoric acid and the following bases, salts of pyrophosphoric acid and the following bases, and salts of polyphosphoric acid and the following bases.
  • bases contained in phosphates include N,N,N',N'-tetramethyldiaminomethane, ethylenediamine, N,N'-dimethylethylenediamine, N,N'-diethylethylenediamine, N,N-dimethyl Ethylenediamine, N,N-diethylethylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N'-diethylethylenediamine, 1,2-propanediamine, 1,3-propanediamine, tetramethylenediamine, penta Methylenediamine, hexamethylenediamine, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, trans-2,5-dimethylpiperazine, 1,4-bis( 2-aminoethyl)piperazine, 1,4-bis(3
  • the phosphorus-containing flame retardant is preferably one or more selected from the group consisting of melamine pyrophosphate, piperazine pyrophosphate, and ammonium polyphosphate.
  • the polypropylene resin composition more preferably contains both a piperazine pyrophosphate salt and a melamine pyrophosphate salt as a phosphorus-containing flame retardant, and even more preferably contains both a piperazine pyrophosphate salt and a melamine pyrophosphate salt, and a polypropylene resin composition.
  • the weight ratio of the melamine pyrophosphate content to the piperazine pyrophosphate content (melamine pyrophosphate/piperazine pyrophosphate) in the composition is preferably 0.25 or more and 1.0 or less.
  • the molar ratio of pyrophosphoric acid and melamine in the melamine pyrophosphate salt is preferably 1:2.
  • the molar ratio of pyrophosphoric acid to piperazine in piperazine pyrophosphate is preferably 1:1.
  • Melamine phosphoric acid salt and melamine polyphosphoric acid salt can be obtained by reacting the corresponding phosphoric acid or polyphosphoric acid, or a salt thereof, with melamine.
  • melamine pyrophosphate and melamine polyphosphate obtained by heating and condensing monomelamine orthophosphate may be used. Salts and polyphosphate melamine salts are preferred.
  • Piperazine phosphate salt and piperazine polyphosphate salt can be obtained by reacting the corresponding phosphoric acid or polyphosphoric acid, or a salt thereof, with piperazine.
  • piperazine pyrophosphate salt and the piperazine polyphosphate salt As the piperazine pyrophosphate salt and the piperazine polyphosphate salt, piperazine pyrophosphate salt and piperazine polyphosphate salt obtained by a method of heating and condensing monomelamine diorthophosphate may be used, and the pyrophosphate obtained by these methods Piperazine salts and polyphosphate piperazine salts are preferred.
  • phosphate commercially available products can be used.
  • examples of commercially available phosphates include ADEKA's "ADEKA STAB FP-2100JC", “ADEKA STAB FP-2200S”, “ADEKA STAB FP-2300S”, “ADEKA STAB FP-2500S”, and Xusen's "XS-FR-”. 8300'', ⁇ XS-FR-8310'', ⁇ XS-FR-8330'', ⁇ FCP-796'' manufactured by Suzuhiro Chemical Co., Ltd., ⁇ EXOLIT AP422'' manufactured by Clariant Japan, and ⁇ EXOLIT AP462''.
  • phosphoric esters examples include aromatic phosphoric esters, aliphatic phosphoric esters, and oligomers or polymers obtained from the aromatic phosphoric esters and the aliphatic phosphoric esters.
  • aromatic phosphate esters include trixylenyl phosphate, tris(phenylphenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, Resorcinol bis(diphenyl phosphate), resorcinol bis(dixylenyl phosphate), resorcinol bis(dicresyl phosphate), hydroquinone bis(dixylenyl phosphate), bisphenol A bis(diphenyl phosphate), and tetrakis(2,6-dimethylphenyl). ) 1,3-phenylene bisphosphate.
  • aliphatic phosphate esters examples include trimethyl phosphate, tributyl phosphate, tri(2-ethylhexyl) phosphate, tributoxyethyl phosphate, monoisodecyl phosphate, and 2-acryloyloxyethylic acid phosphate.
  • phosphoric acid ester As the phosphoric acid ester, commercially available products can be used. Examples of commercially available phosphate esters include ADEKA STAB FP-600 and ADEKA STAB FP-800.
  • metal oxides examples include zinc oxide, magnesium oxide, calcium oxide, silicon dioxide, titanium oxide, manganese oxide (MnO, MnO 2 ), iron oxide (FeO, Fe 2 O 3 , Fe 3 O 4 ), copper oxide. , nickel oxide, tin oxide, aluminum oxide, and calcium aluminate.
  • zinc oxide, magnesium oxide, or calcium oxide is preferable, and zinc oxide is more preferable.
  • the metal oxide may be subjected to any conventionally known suitable surface treatment.
  • Examples of commercially available zinc oxide include Type 2 zinc oxide manufactured by Seido Kagaku Kogyo Co., Ltd., Type 1 zinc oxide manufactured by Mitsui Kinzoku Mining Co., Ltd., Partially coated zinc oxide manufactured by Mitsui Kinzoku Mining Co., Ltd., and Nano Fine 50. (Ultrafine zinc oxide particles with an average particle size of 0.02 ⁇ m: manufactured by Sakai Chemical Industry Co., Ltd.) and NanoFine K (Ultrafine particle zinc oxide coated with zinc silicate with an average particle size of 0.02 ⁇ m: manufactured by Sakai Chemical Industry Co., Ltd.). It will be done.
  • a polyvalent hydroxyl group-containing compound is a compound having two or more hydroxyl groups.
  • Examples of polyvalent hydroxyl group-containing compounds include pentaerythritol, dipentaerythritol, tripentaerythritol, polypentaerythritol with a degree of condensation of 4 or more, trishydroxyethyl isocyanate, polyethylene glycol, glycerin, starch, glucose, cellulose, and sorbitol. can be mentioned.
  • a polyhydric alcohol compound is preferable because it has low water solubility and low hygroscopicity, and pentaerythritol, dipentaerythritol, tripentaerythritol, or polypentaerythritol is more preferable, and pentaerythritol is more preferable. preferable.
  • the content of the component (B) flame retardant in the polypropylene resin composition of the present embodiment is preferably 5% by mass from the viewpoint of improving flame retardancy when the total amount of the polypropylene resin composition is 100% by mass. % or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, from the viewpoint of improving the mechanical properties of the molded article and improving the fluidity of the polypropylene resin composition. It is preferably 50% by mass or less, more preferably 45% by mass or less, even more preferably 40% by mass or less, preferably in the range of 5 to 50% by mass, and more preferably 10 to 35% by mass. range.
  • the content of the flame retardant other than the phosphorus-containing flame retardant that may be contained in the polypropylene resin composition is based on 100% by mass of the polypropylene resin composition.
  • the content is preferably 0 to 30% by weight, more preferably 0 to 20% by weight, even more preferably 0 to 10% by weight, and may be 0% by weight.
  • the polypropylene resin composition of this embodiment contains, in addition to component (A) a polypropylene polymer and component (B) a flame retardant, for example, a flame retardant molded article made of a polypropylene resin composition. From the viewpoint of improving properties, further improving rigidity and impact resistance, it is preferable to further include component (C) glass fiber.
  • the aspect ratio of the component (C) glass fiber that may be included in the polypropylene resin composition of the present embodiment is usually 20 to 60, preferably 25 or more, more preferably 30 or more, and preferably 58 or less. and more preferably 55 or less.
  • An example of a method for adjusting the aspect ratio of the component (C) glass fiber that may be included in the polypropylene resin composition to the suitable aspect ratio described above is a glass fiber extruder when kneading raw materials in an extruder. Extruder temperature; screw rotation speed; melt flow rate of polypropylene polymer as raw material; length (fiber length) and fiber diameter of glass fiber as raw material; .
  • the length of the component (C) glass fiber is preferably 200 ⁇ m or more, more preferably 300 ⁇ m or more, preferably 600 ⁇ m or less, and more as a weight average fiber length based on 200 fibers. It is preferably 550 ⁇ m or less, preferably 200 to 600 ⁇ m.
  • the length and diameter of the glass fiber can be measured, for example, by observation using a microscope.
  • Component (C) glass fibers may contain, for example, two or more types of glass fibers with different aspect ratios in any proportion. That is, as the glass fiber that may be included in the polypropylene resin composition, only one type of glass fiber may be used, or two or more types of glass fibers having different characteristics, aspect ratios, etc. may be used.
  • component (C) glass fiber commercially available glass fiber can be used.
  • the material of component (C) glass fiber is not particularly limited.
  • any conventionally known suitable glass can be used.
  • the glass fiber material include E glass (alkali-free glass), A glass, C glass, S glass, and D glass, with E glass being preferred.
  • Glass fibers can be manufactured by any conventionally known suitable manufacturing method. The glass fibers may be surface treated with a sizing agent and/or a surface treatment agent.
  • the component (C) glass fiber it is preferable to use a glass fiber whose surface has been treated with a surface treatment agent from the viewpoint of improving the dispersibility in the component (A) polypropylene polymer.
  • suitable surface treating agents include organosilane coupling agents, titanate coupling agents, aluminate coupling agents, zirconate coupling agents, silicone compounds, higher fatty acids, fatty acid metal salts, and fatty acid esters.
  • organic silane coupling agents examples include vinyltrimethoxysilane, ⁇ -chloropropyltrimethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane, ⁇ -aminopropyltrimethoxysilane, and 3-acryloxypropyltrimethoxysilane. Can be mentioned.
  • titanate coupling agents examples include isopropyl triisostearoyl titanate, isopropyl tris(dioctylpyrophosphate) titanate, and isopropyl tri(N-aminoethyl) titanate.
  • aluminate coupling agents examples include acetalkoxyaluminum diisopropylate.
  • zirconate coupling agents examples include tetra(2,2-diallyloxymethyl)butyl, di(tridecyl)phosphite zirconate, and neopentyl(diallyl)oxytrineodecanoyl zirconate.
  • silicone compounds examples include silicone oil and silicone resin.
  • higher fatty acids examples include oleic acid, capric acid, lauric acid, palmitic acid, stearic acid, montanic acid, linoleic acid, rosin acid, linolenic acid, undecanoic acid, and undecenoic acid.
  • higher fatty acid metal salts include sodium salts, lithium salts, calcium salts, magnesium salts, zinc salts, and aluminum salts of fatty acids having 9 or more carbon atoms (eg, stearic acid, montanic acid).
  • preferred higher fatty acid metal salts are calcium stearate, aluminum stearate, calcium montanate, and sodium montanate.
  • fatty acid esters examples include polyhydric alcohol fatty acid esters such as glycerin fatty acid esters, alpha sulfo fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbitan fatty acid esters, polyethylene fatty acid esters, and sucrose fatty acid esters.
  • polyhydric alcohol fatty acid esters such as glycerin fatty acid esters, alpha sulfo fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbitan fatty acid esters, polyethylene fatty acid esters, and sucrose fatty acid esters.
  • the amount of surface treatment agent used is not particularly limited.
  • the amount of surface treatment agent used is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 3 parts by weight, based on 100 parts by weight of glass fiber.
  • Component (C) glass fibers may be treated with a sizing agent.
  • a sizing agent By treatment with a sizing agent, the glass fibers can be bound together.
  • sizing agents include epoxy sizing agents, aromatic urethane sizing agents, aliphatic urethane sizing agents, acrylic sizing agents, and maleic anhydride-modified polyolefin sizing agents.
  • the sizing agent it is preferable to use a sizing agent that can be melted at the temperature of melt-kneading with the component (A) polypropylene polymer, and it is more preferable to use a sizing agent that melts at 200° C. or lower.
  • a so-called chopped strand glass fiber obtained by cutting a glass strand may be used. From the viewpoint of improving the rigidity of a molded article formed from a polypropylene resin composition and further improving its impact strength, it is preferable to use chopped strand glass fiber.
  • glass fibers resin pellets containing glass fibers (glass fiber-containing resin pellets) may be used.
  • the length of the glass fibers fiber length
  • fiber length generally corresponds to the length of the resin pellet in the extrusion direction.
  • Glass fiber-containing resin pellets can be produced by any conventionally known suitable production method. Specifically, glass fiber-containing resin pellets can be manufactured by, for example, a pultrusion method. The pultrusion method is usually a method in which multiple continuous glass fibers are drawn out, and resin is melted and extruded from a resin extruder to impregnate the glass fiber bundle, thereby integrating the multiple glass fiber bundles. . Glass fiber-containing resin pellets can be produced by generally cooling a bundle of glass fibers impregnated with resin and cutting them with a pelletizer.
  • the content of glass fiber in the glass fiber-containing resin pellet is preferably 50 to 99.9% by mass.
  • the content of component (C) glass fiber in the polypropylene resin composition of the present embodiment is preferably 5% by mass or more, more preferably 8% by mass when the total amount of the polypropylene resin composition is 100% by mass. % by mass or more, more preferably 10% by mass or more, preferably 50% by mass or less, more preferably 45% by mass or less, still more preferably 35% by mass or less, preferably 5 to 45% by mass. It is in the range of % by mass.
  • component (D) Acid-modified polyolefin polymer
  • the polypropylene resin composition of this embodiment can improve the properties of a molded article and also improve the (aesthetic) appearance of the molded article, so component (A )
  • component (B) a flame retardant, and further component (C) glass fiber, it is preferable to further include component (D) an acid-modified polyolefin polymer.
  • the acid-modified polyolefin polymer refers to a polymer obtained by modifying a polyolefin polymer with an unsaturated carboxylic acid and/or an unsaturated carboxylic acid derivative.
  • acid-modified polyolefin polymers examples include acid-modified polyethylene polymers and acid-modified polypropylene polymers.
  • the acid-modified polyethylene polymer means a polymer obtained by modifying a polyethylene polymer with an unsaturated carboxylic acid and/or an unsaturated carboxylic acid derivative.
  • the acid-modified polypropylene polymer refers to a polymer obtained by modifying a polypropylene polymer with an unsaturated carboxylic acid and/or an unsaturated carboxylic acid derivative.
  • polystyrene resin As the polyolefin polymer to be subjected to acid modification to produce an acid-modified polypropylene polymer, a homopolymer of one type of olefin or a copolymer of two or more types of olefins can be used.
  • polyolefin polymers include polyethylene polymers and polypropylene polymers.
  • the polyethylene polymer to be subjected to acid modification preferably contains more than 50% by mass of ethylene units based on the total structural units of the polymer, and the ethylene units in the polyethylene polymer are usually It is 100% by mass or less.
  • the polypropylene polymer to be subjected to acid modification is a polypropylene polymer containing more than 50% by mass of propylene units based on the total constituent units of the polypropylene polymer, and the propylene units in the polypropylene polymer are It is usually 100% by mass or less.
  • Examples of the polypropylene polymer to be subjected to acid modification are the same as the examples and preferred examples already described as the component (A) polypropylene polymer.
  • An acid-modified polypropylene polymer is usually a polymer having a partial structure of a polypropylene polymer and a partial structure derived from an unsaturated carboxylic acid and/or an unsaturated carboxylic acid derivative.
  • acid-modified polypropylene polymers include (i) a polymer obtained by graft polymerizing an unsaturated carboxylic acid and/or an unsaturated carboxylic acid derivative to a propylene homopolymer; (ii) a polymer obtained by graft polymerizing a propylene homopolymer with an unsaturated carboxylic acid and/or an unsaturated carboxylic acid derivative; An unsaturated carboxylic acid and/or an unsaturated carboxylic acid derivative is graft-polymerized to a copolymer obtained by copolymerizing one or more monomers selected from the group consisting of ⁇ -olefins having 4 or more carbon atoms.
  • a block copolymer obtained by homopolymerizing propylene and then copolymerizing one or more monomers selected from the group consisting of ethylene and an ⁇ -olefin having 4 or more carbon atoms examples include modified polypropylene polymers obtained by graft polymerizing unsaturated carboxylic acids and/or unsaturated carboxylic acid derivatives.
  • the polypropylene polymer to be subjected to acid modification may be a single type of polypropylene polymer or may contain a combination of two or more types of polypropylene polymers in any ratio.
  • the acid-modified polypropylene polymer to be subjected to acid modification may be the heterophasic propylene polymer material described above.
  • unsaturated carboxylic acids examples include maleic acid, fumaric acid, itaconic acid, acrylic acid, and methacrylic acid.
  • unsaturated carboxylic acid derivatives include acid anhydrides, ester compounds, amide compounds, imide compounds, and metal salts of unsaturated carboxylic acids.
  • Specific examples of unsaturated carboxylic acid derivatives include maleic anhydride, itaconic anhydride, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-hydroxyethyl methacrylate, Maleic acid monoethyl ester, maleic acid diethyl ester, fumaric acid monomethyl ester, fumaric acid dimethyl ester, acrylamide, methacrylamide, maleic acid monoamide, maleic acid diamide, fumaric acid monoamide, maleimide, N-butylmaleimide, and sodium methacrylate. Can be mentioned.
  • unsaturated carboxylic acid maleic acid and acrylic acid are preferred.
  • unsaturated carboxylic acid derivatives maleic anhydride and 2-hydroxyethyl methacrylate are preferred.
  • the acid-modified polypropylene polymer it is preferable to use the already explained polymers (ii) and (iii).
  • acid-modified polyolefin polymer (acid-modified polypropylene polymer)
  • maleic anhydride is graft-polymerized to a polyolefin polymer containing more than 50% by mass of propylene units in all structural units.
  • An acid-modified polyolefin polymer obtained by is preferred.
  • the total content of unsaturated carboxylic acid units and unsaturated carboxylic acid derivative units in the acid-modified polyolefin-based polymer is determined from the viewpoint of improving the rigidity and hardness of the molded article formed from the polypropylene-based resin composition.
  • the amount of the polymer is 100% by mass, it is preferably 0.1 to 20% by mass, more preferably 0.1 to 10% by mass.
  • the acid-modified polyolefin polymer contains only one of unsaturated carboxylic acid units and unsaturated carboxylic acid derivative units, the total content refers to the one type of unit. means the content of
  • the content of unsaturated carboxylic acid units and unsaturated carboxylic acid derivative units is the value calculated by quantifying the absorption based on unsaturated carboxylic acids and unsaturated carboxylic acid derivatives by infrared absorption spectrum or NMR spectrum.
  • the grafting efficiency of the unsaturated carboxylic acid and/or the unsaturated carboxylic acid derivative of the acid-modified polyolefin polymer should be 0.51 or more from the viewpoint of improving the rigidity and impact strength of the molded article formed from the polypropylene resin composition. It is preferable that there be.
  • “Grafting efficiency of acid-modified polyolefin polymer” refers to “the unsaturated carboxylic acid and/or unsaturated carboxylic acid derivative contained in the acid-modified polyolefin polymer that is chemically bonded to the acid-modified polyolefin polymer.” The amount of unsaturated carboxylic acids and/or unsaturated carboxylic acids chemically bonded to the acid-modified polyolefin polymer relative to the total amount of unsaturated carboxylic acids and/or unsaturated carboxylic acid derivatives not chemically bonded to the acid-modified polyolefin polymer. "ratio of the amounts of saturated carboxylic acid derivatives". Grafting efficiency in graft polymerization of unsaturated carboxylic acids and/or unsaturated carboxylic acid derivatives can be determined by the following procedures (1) to (9).
  • the content (X1) of the unsaturated carboxylic acid derivative is calculated.
  • (8) Separately, perform the above steps (5) to (6) on the acid-modified polyolefin polymer that has not been purified, and from the infrared absorption spectrum, Calculate the content (X2) of the unsaturated carboxylic acid and/or unsaturated carboxylic acid derivative (here, the content (X2) is the unsaturated carboxylic acid and/or unsaturated carboxylic acid derivative that has reacted with the polypropylene polymer).
  • the melt flow rate of the acid-modified polypropylene polymer is preferably 5 to 400 g/10 minutes, more preferably 10 to 200 g/10 minutes, and particularly preferably 20 g/10 minutes. ⁇ 200g/10 minutes.
  • the polypropylene resin composition of the present embodiment includes the already explained component (A) polypropylene polymer, component (B) flame retardant, component (C) glass fiber, and component (D) acid-modified component.
  • component (A) polypropylene polymer includes the already explained component (A) polypropylene polymer, component (B) flame retardant, component (C) glass fiber, and component (D) acid-modified component.
  • component (B) flame retardant component (B) flame retardant, component (C) glass fiber, and component (D) acid-modified component.
  • component (C) glass fiber includes component (C) glass fiber, and component (D) acid-modified component.
  • component (D) acid-modified component includes the already explained component (A) polypropylene polymer, component (B) flame retardant, component (C) glass fiber, and component (D) acid-modified component.
  • the polyolefin may further contain arbitrary components.
  • polypropylene resin composition of the present embodiment may further include include neutralizing agents, antioxidants, elastomers, ultraviolet absorbers, lubricants, antistatic agents, anti-blocking agents, processing aids, organic Peroxides, colorants (inorganic pigments, organic pigments, etc.), pigment dispersants, foaming agents, foaming nucleating agents, plasticizers, crosslinking agents, crosslinking aids, brightness agents, antibacterial agents, and light diffusing agents. Can be mentioned.
  • the polypropylene resin composition of the present embodiment may contain one of the above arbitrary components, or may contain a combination of two or more arbitrary components in any ratio.
  • An example of an elastomer that can be included in the polypropylene resin composition of the present embodiment is a random copolymer having an ethylene unit and an ⁇ -olefin unit having 4 to 10 carbon atoms.
  • the random copolymer preferably has a melt flow rate of 0.1 to 50 g/10 min as measured in accordance with JIS K7210-1:2014 and K7210-2:2014 at 230°C and under a load of 2.16 kgf. It is.
  • the ⁇ -olefin having 4 to 10 carbon atoms constituting the random copolymer that is an elastomer is the same as the ⁇ -olefin having 4 to 10 carbon atoms which can constitute the polypropylene polymer component (A) described above.
  • ⁇ -olefins such as Specific examples of the ⁇ -olefin include ⁇ -olefins having a chain structure such as 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, and 1-decene, and vinyl Examples include ⁇ -olefins having a cyclic structure such as cyclopropane and vinylcyclobutane. As the ⁇ -olefin, 1-butene, 1-hexene and 1-octene are preferred.
  • random copolymers that are elastomers include ethylene-1-butene random copolymer, ethylene-1-hexene random copolymer, ethylene-1-octene random copolymer, and ethylene-1-decene random copolymer.
  • examples include ethylene-(3-methyl-1-butene) random copolymers, and copolymers of ethylene and an ⁇ -olefin having a cyclic structure.
  • the content of ⁇ -olefin in the random copolymer is preferably 1 to 49% by mass, more preferably 5 to 49% by mass, when the weight of the random copolymer is 100% by mass, and Preferably it is 24 to 49% by mass.
  • the density of the random copolymer is preferably 0.850 to 0.890 g/cm 3 , more preferably 0.850 to 0.890 g/cm 3 from the viewpoint of improving the impact resistance of a molded article made of a polypropylene resin composition. It is 850 to 0.880 g/cm 3 , more preferably 0.855 to 0.867 g/cm 3 .
  • a random copolymer that is an elastomer can be produced by polymerizing monomers using a polymerization catalyst.
  • the polymerization catalyst include the catalysts mentioned above as examples of polymerization catalysts for producing polypropylene polymers.
  • a commercially available product may be used as the random copolymer.
  • Examples of commercial products that are random copolymers that are elastomers include Engage (registered trademark) manufactured by Dow Chemical Japan Co., Ltd., Tafmer (registered trademark) manufactured by Mitsui Chemicals, Neozex (registered trademark) manufactured by Prime Polymer, and Ultozex (registered trademark), Excellen FX (registered trademark), Sumikasen (registered trademark), and Espren SPO (registered trademark) manufactured by Sumitomo Chemical Co., Ltd.
  • the content of the elastomer in the polypropylene resin composition is preferably 0 to 30% by mass, more preferably 0 to 10% by mass, based on 100% by mass of the polypropylene resin composition. In this embodiment, the content of the elastomer in the polypropylene resin composition may be 5 to 30% by mass.
  • the polypropylene resin composition of the present embodiment has a melt flow rate measured at 230° C. and a load of 2.16 kgf, preferably 0.1 g/10 minutes or more, and more preferably is 1 g/10 minutes or more, preferably 400 g/10 minutes or less, more preferably 300 g/10 minutes or less, and even more preferably 200 g/10 minutes or less.
  • melt flow rate of the polypropylene resin composition is below the upper limit of the above range, the flame retardance of the polypropylene resin composition can be effectively improved, and if the melt flow rate is above the lower limit of the above range, the polypropylene It is possible to improve the weld strength of a molded article formed from the resin composition.
  • molded articles particularly excellent in flame retardance can be manufactured.
  • molded products that can be manufactured include injection molded products, extrusion molded products, compression molded products, irregular molded products, vacuum molded products, sheet molded products, roll molded products, hot press molded products, foam molded products, and injection press molded products.
  • molded bodies, blow molded bodies, and gas injection molded bodies include injection molded products, extrusion molded products, compression molded products, irregular molded products, vacuum molded products, sheet molded products, roll molded products, hot press molded products, foam molded products, and injection press molded products.
  • the polypropylene resin composition of the present embodiment has excellent fluidity during the molding process, it can be particularly suitably applied to the production of injection molded articles, extrusion molded articles, and injection press molded articles, particularly injection molded articles. It can be suitably applied to the production of.
  • the polypropylene resin composition of this embodiment can be produced by any conventionally known suitable method.
  • the polypropylene resin composition is prepared using, for example, a twin-screw kneading extruder equipped with a cylinder and two screws, and the component (A) polypropylene polymer and the component (B) flame retardant, as well as ( It can be produced by kneading component C) glass fiber and component (D) acid-modified polyolefin, as well as optional components added as necessary.
  • the polypropylene resin composition is preferably prepared by feeding raw material (1) containing component (A) a polypropylene polymer and component (B) a flame retardant into a cylinder of a twin-screw kneading extruder. , and can be manufactured by further supplying component (C) glass fiber into a cylinder.
  • the raw material (1) may contain a molecular weight regulator for adjusting the molecular weight of the polypropylene polymer as a further optional component.
  • molecular weight modifiers include organic peroxides.
  • the molecular weight regulator may be contained in the raw material (1) in the form of a masterbatch diluted with any suitable conventionally known resin.
  • the molded object is manufactured by molding a polypropylene resin composition.
  • the molded article obtained by molding the polypropylene resin composition of this embodiment contains the polypropylene resin composition of this embodiment already described, and therefore has particularly excellent flame retardancy.
  • the molded body is assumed to be thin and have a relatively large surface area of about 1 m 2 .
  • the dimensions of the molded body are not particularly limited.
  • the assumed dimensions of the molded body are, for example, external dimensions of 0.5 to 2 m in length, 0.5 to 2 m in width, and 1 to 10 mm in thickness.
  • the molded body is assumed to be, for example, plate-shaped or hollow.
  • the molded body made of the polypropylene resin composition of the present embodiment is made of materials for various parts (e.g., interior and exterior parts of automobiles and engine room interior parts, motorcycle parts, electrical product parts, various containers, It can be suitably used as furniture, containers and packaging members, construction members, and casings for electric vehicle charging stands).
  • Examples of automobile interior and exterior parts include instrument panels, door trims, pillars, side protectors, console boxes, column covers, bumpers, fenders, wheel covers, parts around charging ports, heat insulation mats, sound insulation mats, connectors, and sensor brackets. can be mentioned.
  • Examples of parts inside the engine room of a car include a battery case, engine cover, relay box, bus bar, cell case, and cable cover.
  • Examples of motorcycle parts include cowlings and muffler covers.
  • the method for manufacturing the molded body is not particularly limited.
  • methods for producing the molded body include injection molding.
  • injection molding methods include general injection molding, injection foam molding, supercritical injection foam molding, ultrahigh-speed injection molding, injection compression molding, gas-assisted injection molding, and sandwich molding. , sandwich foam molding method, and insert/outsert molding method.
  • the molded body is preferably an injection molded body molded by an injection molding method from the viewpoint of improving economy and precision.
  • a molded article made of a polypropylene resin composition can be suitably used for the same uses as those already described as uses of the polypropylene resin composition.
  • the evaluation of the flame retardancy of the molded article in this embodiment can be performed using, for example, the UL94-V method (IEC60695-11-10 B method, ASTN D38(01)), and the UL94-5V method (IEC60695-11-20, ASTN D38(01)). D5048).
  • the molded body is made into a test piece of a predetermined size, the test piece is fixed with a clamp, and the test piece is exposed to a predetermined flame for a predetermined time a predetermined number of times.
  • the flame retardancy (combustibility) can be evaluated based on the combustion behavior of the test piece when it is heated.
  • the flame retardance can be evaluated as being good if it falls under "V-0" in the flammability classification.
  • evaluation method The evaluation method in this example is as follows.
  • Measurement was performed at a load of 2.16 kgf and a temperature of 230° C. according to the method specified in JIS K7210-1:2014 and K7210-2:2014.
  • the pellets of the polypropylene resin composition were supplied to an injection molding machine: "SYCAP110" manufactured by Sumitomo Heavy Industries, Ltd., and injection molding was performed under the conditions of a molding temperature of 230 ° C. and a mold cooling temperature of 50 ° C., and the resulting product was 127 mm (length).
  • a test piece in the shape of a plate (cuboid) measuring 13 mm (width) x 1.6 mm (thickness) was prepared. Using the obtained test piece, the flame retardancy of the test piece was evaluated according to the UL94-V method.
  • the flame retardance according to the UL94-V method was evaluated using three levels of flammability classification "V-0, V-1 and V-2".
  • flammability classification V-0 is superior to V-1
  • V-1 is superior to V-2. That is, in the evaluation of flame retardancy according to the UL94-V method according to this example, the flammability classification "V-0" is the most excellent in flame retardancy.
  • the flame retardance was evaluated to be good if it fell under "V-0" in the flammability classification.
  • V-0 falling under the flammability classification "V-0" means that the burning time of the test plate is 10 seconds or less, the total burning time of the 5 test plates is 50 seconds or less, and the combustion time of each test plate is This means that the following conditions are met: a glow time of 30 seconds or less, no combustion up to the clamp, and no cotton ignition due to dripping from the test plate.
  • the polypropylene resin composition was supplied to an injection molding machine: "IS100EN” manufactured by Toshiba Machine Co., Ltd., and injection molding was performed under conditions of a molding temperature of 220 °C and a mold cooling temperature of 50 °C. ) ⁇ 2.0 mm (thickness) test flat plate was prepared.
  • a plaque test was conducted based on the UL94-5V method. Planar shape when viewed in the thickness direction obtained by cutting out the 2.0 mm thick test plate obtained as above into 127 mm (length) x 13 mm (width) x 2.0 mm (thickness)
  • a bar test was conducted on a square test plate based on the UL94-5V method.
  • the flame retardance was evaluated to be good if the results of the plaque test and bar test corresponded to "5V-A" in the flammability classification.
  • the molecular weight was measured by GPC method under the following conditions. Orthodichlorobenzene (dibutylhydroxytoluene was further added by 0.1 w/v as an antioxidant) was used as a solvent, and the concentration of the sample (polypropylene polymer) was 1 mg/mL.
  • HLC-8121GPC/HT manufactured by Tosoh Corporation (or manufactured by Tosoh Corporation, HLC-8321GPC/HT) was used.
  • the measurement column was a GPC column manufactured by Tosoh Corporation, TSKgel GMHHR-H(S)HT 7.5mm I. D. Three ⁇ 300 mm were connected and used.
  • the mobile phase was orthodichlorobenzene (0.1 w/v of dibutylhydroxytoluene was added as an antioxidant), the flow rate was 1 mL/min, the column oven temperature was set to 140 °C, and the autosampler temperature was set to 140 °C. and the system oven temperature was set to 40°C.
  • a differential refractive index detector (RID) was used as a detector, the RID cell temperature was 140° C., and the amount of sample solution injected was 300 ⁇ L. The obtained measured value was multiplied by a Q factor value of 41.3 to obtain the molecular weight in terms of polystyrene.
  • the ratio of components with a molecular weight (M) of 2,000,000 or more and the ratio of components with a molecular weight (M) of 50,000 or less were calculated based on the integral value of the molecular weight distribution curve obtained by GPC measurement. .
  • the following raw materials were used.
  • Ingredient (A-1) MFR: (230°C, load 2.16 kgf): 0.5 g/10 min Ratio of components with molecular weight (M) of 2,000,000 or more: 5.1 wt% Ratio of components whose molecular weight (M) is 50,000 or less: 4.2wt%
  • Ingredient (A-2) MFR: (230°C, load 2.16kgf): 8g/10min Ratio of components with molecular weight (M) of 2,000,000 or more: 0.9wt% Ratio of components whose molecular weight (M) is 50,000 or less: 10.9wt%
  • Ingredient (A-3) MFR: (230°C, load 2.16kgf): 18g/10min Ratio of components with molecular weight (M) of 2,000,000 or more: 0.5wt% Ratio of components whose molecular weight (M) is 50,000 or less: 15.0wt%
  • Ingredients (A-4) MFR: (230°C, load 2.16kgf): 120g/10min Ratio of components with molecular weight (M) of 2,000,000 or more: 0.0wt% Ratio of components whose molecular weight (M) is 50,000 or less: 23.5wt%
  • Ingredients (A-5) MFR: (230°C, load 2.16kgf): 240g/10min Ratio of components with molecular weight (M) of 2,000,000 or more: 0.0wt% Ratio of components whose molecular weight (M) is 50,000 or less: 38.7wt%
  • liquid propylene, triethylaluminum, tert-butyl-n-propyldimethoxysilane, and a polymerization catalyst are continuously supplied to a first reaction vessel made of stainless steel to produce a first propylene reaction vessel.
  • a first step of polymerizing polymer component (a) was carried out.
  • the polymerization catalyst and the first propylene polymer component (a) are transferred to a second reaction vessel connected in series to the first reaction vessel, and further propylene and hydrogen are added.
  • a second step was carried out in which a second propylene polymer component (b) having a different molecular weight from the first propylene polymer component (a) was polymerized while supplying the first propylene polymer component (a).
  • B-1) and (B-2) Flame retardant
  • B-2) Product name: ADEKA STAB FP-2500S (manufactured by ADEKA)
  • B-2) Product name: ADEKA STAB FP-2300S (manufactured by ADEKA)
  • Component (C) Glass fiber The following glass fiber was used as the component (C) glass fiber.
  • Glass fiber (chopped strand) Product name: ESC03T-480H (manufactured by Nippon Electric Glass Co., Ltd.) Diameter: 10 ⁇ m Fiber length: 3mm
  • the premix was fed through the feed port of a twin-screw extruder and kneaded to obtain a maleic anhydride-modified polypropylene polymer.
  • the maleic anhydride-modified polypropylene polymer as the acid-modified polypropylene polymer obtained has an MFR (230° C., load 2.16 kgf) of 170 g/10 minutes, and a content of maleic anhydride units of 0.32. (mass%).
  • Example 1 Manufacture of polypropylene resin composition
  • the composition (content) shown in Table 1 below includes component (A) polypropylene polymer, component (B) flame retardant, and calcium stearate (product name: Calcium Stearate S, manufactured by NOF Corporation) as a neutralizing agent. 0.05 parts by mass and 3,9-bis[2-(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl]- as an antioxidant.
  • the amount of the neutralizing agent and antioxidant used is the value when the total weight of component (A) and component (B) is 100 parts by mass.
  • a flammability test was conducted using the obtained pellets to evaluate flame retardancy. Specifically, as already explained, a test plate was formed and the flame retardancy was evaluated by the UL94-V method (including the evaluation of the presence or absence of drip in the UL94-V method. The same applies hereinafter). The results are shown in Table 1.
  • Example 1 Pellets of a polypropylene resin composition were obtained in the same manner as in Example 1 described above, and flame retardancy was evaluated by the UL94-V method. The results are shown in Table 1.
  • Example 9 Manufacture of polypropylene resin composition
  • the composition shown in Table 2 below consists of component (A) polypropylene polymer, component (B) (phosphorus-containing) flame retardant, component (D) acid-modified polypropylene polymer, and calcium stearate (product) as a neutralizing agent.
  • component (A) polypropylene polymer component (B) (phosphorus-containing) flame retardant, component (D) acid-modified polypropylene polymer, and calcium stearate (product) as a neutralizing agent.
  • Component (C) glass fiber is fed into the kneaded product obtained by melt-kneading from a side feeder installed in the middle of a twin-screw kneading extruder in the composition shown in Table 2 below, and is further kneaded. After extrusion, the extrudate was passed through a cold water bath to form strands, and then the strands were cut with a strand cutter to obtain pellets.
  • the amount of neutralizing agent and antioxidant used is determined by the amount of component (A) polypropylene polymer, component (B) flame retardant, component (C) glass fiber, and component (D) acid-modified polyolefin polymer. This is the amount when the total weight is 100 parts by mass.
  • Example 10 to 11 Pellets of a polypropylene resin composition were obtained in the same manner as in Example 9 described above, and flame retardancy was evaluated by the UL94-V method and the UL94-5V method. The results are shown in Table 2.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition de résine de polypropylène qui contient un polymère de polypropylène (composant (A)) et un retardateur de flamme (composant (B)), le polymère de polypropylène (composant (A)) satisfaisant la condition (a-1) et la condition (a-2) décrite ci-dessous. Condition (a-1): Par rapport à la quantité totale du polymère de polypropylène (composant (A)), la proportion du composant qui a un poids moléculaire (M) de 2,000,000 ou plus tel que déterminé sur la base de la courbe de distribution de poids moléculaire obtenue par mesure par GPC est de 0,6 % en masse ou plus. Condition (a-2): Par rapport à la quantité totale du polymère de polypropylène (composant (A)), la proportion du composant qui a un poids moléculaire (M) de 50,000 ou moins tel que déterminé sur la base de la courbe de distribution de poids moléculaire obtenue par mesure par GPC est de 16% en masse ou plus.
PCT/JP2023/021504 2022-08-05 2023-06-09 Composition de résine de polypropylène et corps moulé la contenant WO2024029197A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008074896A (ja) * 2006-09-19 2008-04-03 Japan Polypropylene Corp ポリプロピレン系樹脂組成物
JP2009275073A (ja) * 2008-05-13 2009-11-26 Japan Polypropylene Corp 難燃性ポリプロピレン樹脂組成物
JP2015078276A (ja) * 2013-10-16 2015-04-23 日本ポリプロ株式会社 ポリプロピレン系難燃樹脂組成物
WO2021100603A1 (fr) * 2019-11-19 2021-05-27 Ｍｃｐｐイノベーション合同会社 Composition d'élastomère thermoplastique, et corps moulé de celle-ci
WO2022030480A1 (fr) * 2020-08-06 2022-02-10 住友化学株式会社 Composition de résine à base de polypropylène et objet moulé la comprenant

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008074896A (ja) * 2006-09-19 2008-04-03 Japan Polypropylene Corp ポリプロピレン系樹脂組成物
JP2009275073A (ja) * 2008-05-13 2009-11-26 Japan Polypropylene Corp 難燃性ポリプロピレン樹脂組成物
JP2015078276A (ja) * 2013-10-16 2015-04-23 日本ポリプロ株式会社 ポリプロピレン系難燃樹脂組成物
WO2021100603A1 (fr) * 2019-11-19 2021-05-27 Ｍｃｐｐイノベーション合同会社 Composition d'élastomère thermoplastique, et corps moulé de celle-ci
WO2022030480A1 (fr) * 2020-08-06 2022-02-10 住友化学株式会社 Composition de résine à base de polypropylène et objet moulé la comprenant

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