WO2022030480A1 - ポリプロピレン系樹脂組成物及びそれを含む成形体 - Google Patents
ポリプロピレン系樹脂組成物及びそれを含む成形体 Download PDFInfo
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- WO2022030480A1 WO2022030480A1 PCT/JP2021/028749 JP2021028749W WO2022030480A1 WO 2022030480 A1 WO2022030480 A1 WO 2022030480A1 JP 2021028749 W JP2021028749 W JP 2021028749W WO 2022030480 A1 WO2022030480 A1 WO 2022030480A1
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- Prior art keywords
- polypropylene
- polymer
- propylene
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- resin composition
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- NKHAVTQWNUWKEO-NSCUHMNNSA-N monomethyl fumarate Chemical compound COC(=O)\C=C\C(O)=O NKHAVTQWNUWKEO-NSCUHMNNSA-N 0.000 description 1
- UDGSVBYJWHOHNN-UHFFFAOYSA-N n',n'-diethylethane-1,2-diamine Chemical compound CCN(CC)CCN UDGSVBYJWHOHNN-UHFFFAOYSA-N 0.000 description 1
- VGIVLIHKENZQHQ-UHFFFAOYSA-N n,n,n',n'-tetramethylmethanediamine Chemical compound CN(C)CN(C)C VGIVLIHKENZQHQ-UHFFFAOYSA-N 0.000 description 1
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- SXJVFQLYZSNZBT-UHFFFAOYSA-N nonane-1,9-diamine Chemical compound NCCCCCCCCCN SXJVFQLYZSNZBT-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000002667 nucleating agent Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- MWFNQNPDUTULBC-UHFFFAOYSA-N phosphono dihydrogen phosphate;piperazine Chemical compound C1CNCCN1.OP(O)(=O)OP(O)(O)=O MWFNQNPDUTULBC-UHFFFAOYSA-N 0.000 description 1
- NQQWFVUVBGSGQN-UHFFFAOYSA-N phosphoric acid;piperazine Chemical compound OP(O)(O)=O.C1CNCCN1 NQQWFVUVBGSGQN-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 230000001012 protector Effects 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- SONHXMAHPHADTF-UHFFFAOYSA-M sodium;2-methylprop-2-enoate Chemical compound [Na+].CC(=C)C([O-])=O SONHXMAHPHADTF-UHFFFAOYSA-M 0.000 description 1
- YKIBJOMJPMLJTB-UHFFFAOYSA-M sodium;octacosanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCCCCCCCCCCCC([O-])=O YKIBJOMJPMLJTB-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 235000010356 sorbitol Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000005720 sucrose Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- LVEOKSIILWWVEO-UHFFFAOYSA-N tetradecyl 3-(3-oxo-3-tetradecoxypropyl)sulfanylpropanoate Chemical compound CCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCC LVEOKSIILWWVEO-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
- KOWVWXQNQNCRRS-UHFFFAOYSA-N tris(2,4-dimethylphenyl) phosphate Chemical compound CC1=CC(C)=CC=C1OP(=O)(OC=1C(=CC(C)=CC=1)C)OC1=CC=C(C)C=C1C KOWVWXQNQNCRRS-UHFFFAOYSA-N 0.000 description 1
- WTLBZVNBAKMVDP-UHFFFAOYSA-N tris(2-butoxyethyl) phosphate Chemical compound CCCCOCCOP(=O)(OCCOCCCC)OCCOCCCC WTLBZVNBAKMVDP-UHFFFAOYSA-N 0.000 description 1
- QEEHNBQLHFJCOV-UHFFFAOYSA-N tris(2-phenylphenyl) phosphate Chemical compound C=1C=CC=C(C=2C=CC=CC=2)C=1OP(OC=1C(=CC=CC=1)C=1C=CC=CC=1)(=O)OC1=CC=CC=C1C1=CC=CC=C1 QEEHNBQLHFJCOV-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 description 1
- 235000019352 zinc silicate Nutrition 0.000 description 1
Images
Classifications
-
- 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
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/016—Flame-proofing or flame-retarding additives
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0066—Flame-proofing or flame-retarding additives
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/016—Additives defined by their aspect ratio
Definitions
- the present invention relates to a polypropylene-based resin composition and a molded product containing the same.
- the embossment of the glass fiber from the surface is reduced, and the polypropylene-based resin composition capable of producing a molded product having excellent flame retardancy and the embossment of the glass fiber from the surface are reduced. It is an object of the present invention to provide a molded product having excellent flame retardancy.
- the present invention provides the following.
- D acid-modified polyolefin-based polymer
- the content of the flame retardant (B) is 5 to 50% by weight
- the content of the glass fiber (C) is 5 to 40% by weight.
- [5] A molded product containing the polypropylene-based resin composition according to any one of [1] to [4].
- [6] The molded product according to [5], wherein the outer dimensions are 0.5 to 2 m in length, 0.5 to 2 m in width, and 1 to 10 mm in thickness.
- the present disclosure includes the following manufacturing methods.
- [8] The method for producing a polypropylene-based resin composition according to any one of [1] to [5].
- the raw material (1) is supplied into the cylinder at a distance L1 from the position of the end on the upstream side of the two screws, and the glass fiber (C) is supplied into the cylinder with the two screws.
- Polypropylene resin composition in which L1 / L is in the range of 0 or more and less than 0.3 and L2 / L is in the range of 0.3 to 0.9. How to make things.
- a polypropylene-based resin composition capable of producing a molded product having reduced embossment of glass fibers and excellent flame retardancy, and embossing of glass fibers are reduced and excellent in flame retardancy.
- 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 ultimate viscosity number (unit: dL / g) is a value measured at a temperature of 135 ° C. using tetralin as a solvent by the following method. Using a Ubbelohde viscometer, the reduced viscosities are measured for multiple concentrations, the reduced viscosities are plotted against the concentrations, and the ultimate viscosity number is determined by the "extrapolation method" in which the concentrations are extrapolated to zero.
- the polypropylene-based resin composition according to one embodiment of the present invention contains a polypropylene-based polymer (A), a flame retardant (B), and a glass fiber (C) having an aspect ratio of 20 to 60.
- the molded product of the polyproprene-based resin composition of the present embodiment has excellent flame retardancy and a good appearance.
- the polypropylene-based resin composition of the present embodiment is also simply referred to as a resin composition.
- the polypropylene-based polymer is a polymer containing propylene units in an amount of 50% by weight or more based on all the constituent units of the polymer.
- the propylene unit in the polypropylene-based polymer is usually 100% by weight or less.
- Examples of polypropylene-based polymers include propylene homopolymers; and copolymers of propylene and other monomers copolymerizable therewith.
- the above-mentioned copolymer may be a random copolymer or a block copolymer.
- the polypropylene-based resin composition may contain one kind of polypropylene-based polymer alone, or may contain two or more kinds of polypropylene-based polymers in any combination of ratios.
- Examples of a single polypropylene-based polymer are propylene homopolymers; and random copolymers of propylene and other monomers copolymerizable therewith (hereinafter, also referred to as polypropylene-based random copolymers).
- Examples of the combination of two or more kinds of polypropylene-based polymers include a combination of two or more kinds of propylene homopolymers having different weight average molecular weights and the like; a combination of the following polymers (I) and polymer (II). ..
- the polymer (I) is a polymer having a propylene unit in an amount of more than 80% by weight and 100% by weight or less based on the amount of all the constituent units, and the polymer (II) is a propylene unit, an ethylene unit and a polymer. It is a polymer with 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 another monomer.
- the polymer (I) and the polymer (II) may each be a single polymer or a combination of two or more polymers.
- the polypropylene-based polymer is preferably one or more selected from the group consisting of a propylene homopolymer and a heterophasic propylene polymer material from the viewpoint of improving the rigidity and impact resistance of the molded product containing the resin composition. , More preferably a propylene homopolymer.
- the polypropylene-based polymer preferably has an isotactic pentad fraction (also referred to as [mm mm] fraction) measured by 13 C-NMR from the viewpoint of improving the rigidity of the molded product containing the resin composition. It is 0.97 or more, more preferably 0.98 or more. The closer the isotactic pentad fraction of the polypropylene-based polymer is to 1, the higher the stereoregularity of the molecular structure of the polypropylene-based polymer and the higher the crystallinity of the polypropylene-based polymer. When the polypropylene-based polymer is a copolymer, the isotactic pentad fraction can be measured for the chain of propylene units in the copolymer.
- the polypropylene-based polymer was 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 molding processability of the resin composition.
- the melt flow rate (MFR) is preferably 1 g / 10 minutes or more, more preferably 10 g / 10 minutes or more, preferably 500 g / 10 minutes or less, and further preferably 10 g / 10 minutes to 300 g / 10. Minutes.
- the polypropylene-based polymer can be produced, for example, by the following polymerization method using a polymerization catalyst.
- polymerization catalyst examples include a Cheegler-type catalytic system; a Cheegler-Natta-type catalytic system; a catalytic system containing a transition metal compound of Group 4 of the Periodic Table having a cyclopentadienyl ring and an alkylaluminoxane; a cyclopentadienyl ring.
- a catalytic system containing a transition metal compound of Group 4 of the Periodic Table, a compound that reacts with the transition metal compound to form an ionic complex, and an organic aluminum compound examples thereof include a catalytic system in which a group 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 the 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 the catalyst system include JP-A-61-218606, JP-A-5-194685, JP-A-7-216017, JP-A-9-316147, and JP-A-10-212319. Examples thereof include the catalyst system described in JP-A-2004-182981.
- the polymerization method examples 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 propylene homopolymer has a limit viscosity number [ ⁇ ] of preferably 0.1 to 2 dL / 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. It is g, more preferably 0.5 to 1.5 dL / g, still more preferably 0.7 to 1.4 dL / g.
- the ultimate viscosity number [ ⁇ ] is a numerical value measured in tetralin at 135 ° C.
- Polypropylene-based random copolymer An example of a polypropylene-based random copolymer is a random copolymer containing a propylene unit and an ethylene unit (hereinafter, also referred to as a random copolymer (1)); a propylene unit and a carbon atom number of 4 or more.
- a random copolymer containing an ⁇ -olefin unit hereinafter, also referred to as a random polymer (2)
- a propylene unit, an ethylene unit, and an ⁇ -olefin unit having 4 or more carbon atoms examples thereof include a random copolymer (hereinafter, also referred to as a random polymer (3)).
- the ⁇ -olefin having 4 or more carbon atoms that can constitute a polypropylene-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. Examples include polymers.
- Examples of the random copolymer (3) include a propylene-ethylene-1-butene copolymer, a propylene-ethylene-1-hexene copolymer, a propylene-ethylene-1-octene copolymer, and a propylene-ethylene-.
- Examples include 1-decene copolymers.
- the content of the ethylene unit in the random copolymer (1) is preferably 0.1 to 40% by weight, more preferably 0.1 to 30% by weight, still more preferably 2 to 15% by weight.
- the content of the ⁇ -olefin unit having 4 or more carbon atoms in the random copolymer (2) is preferably 0.1 to 40% by weight, more preferably 0.1 to 30% by weight, still more preferable. Is 2 to 15% by weight.
- 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 weight, more preferably 0.1 to 30% by weight. %, More preferably 2 to 15% by weight.
- the content of the propylene unit in these random copolymers (1) to (3) is preferably 60 to 99.9% by weight, more preferably 70 to 99.9% by weight, still more preferably 85 to 85%, respectively. It is 98% by weight.
- the polymer (I) is a polymer having propylene units in an amount of more than 80% by weight and 100% by weight or less based on the amount of all the constituent units.
- the total content of the monomer units other than the propylene unit in the polymer (I) is usually 0% by weight or more and less than 20% by weight, and is 0% by weight, assuming that the weight of the polymer (I) is 100% by weight. It may be 0.01% by weight or more.
- 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.
- 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 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 weight, with the weight of the polymer (II) being 100% by weight. It is more preferably 20 to 60% by weight.
- Examples of the polymer (II) 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 content of the polymer (II) in the heterophasic propylene polymer material is preferably 1 to 50% by weight, more preferably 1 with the total weight of the polymer (I) and the polymer (II) being 100% by weight. It is about 40% by weight, more preferably 5 to 30% by weight, and particularly preferably 8 to 15% by weight.
- heterophasic propylene polymer material examples include the following combinations of polymers in which the polymer (I) is a propylene homopolymer. Combination of propylene homopolymer and (propylene-ethylene) copolymer; Combination of propylene homopolymer and (propylene-ethylene-1-butene) copolymer; propylene homopolymer and (propylene-ethylene-1-) Combination with hexene) copolymer; Combination of propylene homopolymer and (propylene-ethylene-1-octene) copolymer; Combination of propylene homopolymer and (propylene-1-butene) copolymer; Propylene Combination of homopolymer and (propylene-1-hexene) copolymer; Combination of propylene homopolymer and (propylene-1-octene) copolymer; and combination of propylene homopolymer and (propylene-1-decene) ) Combin
- heterophasic propylene polymer material there is a combination of the following polymers 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) will be described first, and the type of the polymer (II) will be described later.
- the heterophasic propylene polymer material that can be contained in the resin composition is preferably (combination of propylene homopolymer and (propylene-ethylene) copolymer, propylene homopolymer and (propylene-ethylene-1-butene).
- Combination with copolymer combination of (propylene-ethylene) copolymer and (propylene-ethylene) copolymer, combination of (propylene-ethylene) copolymer and (propylene-ethylene-1-butene) copolymer , And a combination of a (propylene-1-butene) copolymer and a (propylene-1-butene) copolymer, more preferably a propylene homopolymer and a (propylene-ethylene) copolymer. It is a combination.
- the ultimate viscosity number of the polymer (II) (hereinafter referred to as [ ⁇ ] II) is preferably 1 to 10 dL / g, more preferably 2 to 10 dL / g, and further preferably 5 to 8 dL. / G.
- the ratio of [ ⁇ ] II to [ ⁇ ] I ([ ⁇ ] II / [ ⁇ ] I) is preferably 1 to 20, more preferably 2 to 10, and even more preferably 2 to 9. be.
- the polypropylene-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 used in the 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. Using the value and the content of each polymer, the ultimate viscosity number of the polymer formed by the subsequent polymerization is calculated.
- 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 polymerization step in the first stage and the polymer (II) is obtained in the polymerization step in the second stage.
- Polymerization consisting of 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 extreme viscosity number ([ ⁇ ] Total) measured by the above method of the material) and the content of the polymer (II) contained in the final polymer, the ultimate viscosity number [ ⁇ ] II of the polymer (II) is determined. , Calculate from 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: Weight ratio of polymer (I) to final polymer XII: Weight ratio of polymer (II) to final polymer Note that XI and XII are obtained from the mass balance at the time of polymerization.
- the weight ratio XII of the polymer (II) to the final polymer may be calculated from the following equation 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 3 or more and less than 7, and more preferably 3 to 5.
- the resin composition contains a flame retardant.
- the resin composition may contain one kind of flame retardant alone, or may contain two or more kinds in any combination of ratios.
- halogen-based flame retardants include organic halogenated aromatic compounds.
- organic halogenated aromatic compound include a halogenated diphenyl compound, a halogenated bisphenol compound, a halogenated bisphenol bis (alkyl ether) compound, and a halogenated phthalimide compound.
- halogenated bisphenol compounds include halogenated bisphenyl alkanes, halogenated bisphenyl ethers, halogenated bisphenyl thioethers, and halogenated bisphenyl sulfones.
- halogenated bisphenol bis (alkyl ether) compounds include brominated bisphenol A (brominated aliphatic ether), brominated bisphenol S (brominated aliphatic ether), and chlorinated bisphenol A (chlorinated aliphatic ether).
- chlorinated bisphenol S (chlorinated aliphatic ether) further specific examples include etherified tetrabromobisphenol A and etherified tetrabromobisphenol S.
- guanidine-based flame retardants examples include guanidine compounds such as guanidine nitride.
- the phosphorus-containing flame retardant is a flame retardant containing a phosphorus atom.
- the resin composition preferably contains a phosphorus-containing flame retardant.
- the resin composition may contain a phosphorus-containing flame retardant alone or in any combination of two or more kinds.
- phosphate and the polyphosphate include a salt of orthophosphoric acid and the following base, a salt of pyrophosphoric acid and the following base, and a salt of polyphosphoric acid and the following base.
- bases that can be contained in phosphates are N, N, N', N'-tetramethyldiaminomethane, ethylenediamine, N, N'-dimethylethylenediamine, N, N'-diethylethylenediamine, N, N-.
- the phosphorus-containing flame retardant is preferably one or more selected from the group consisting of pyrrolate melamine salt, pyrophosphate piperazine salt, and polyphosphate ammonium salt.
- the resin composition more preferably contains both a pyrophosphate piperazine salt and a pyrophosphate melamine salt as a phosphorus-containing flame retardant, and more preferably contains both a pyrophosphate piperazine salt and a pyrophosphate melamine salt, and the resin composition.
- the weight ratio of the pyrophosphate melamine salt content to the pyrophosphate piperazine salt content is preferably 0.25 or more and 1.0 or less.
- the molar ratio of pyrophosphate to melamine of the pyrophosphate melamine salt is preferably 1: 2.
- the molar ratio of piperazine pyrophosphate to piperazine is preferably 1: 1.
- the phosphoric acid piperazine salt and the polyphosphate piperazine salt can be obtained by reacting the corresponding phosphoric acid or polyphosphoric acid or these salts with piperazine, respectively.
- the pyrophosphate piperazine salt and the polyphosphoric acid piperazine salt the pyrophosphate piperazine salt and the polyphosphoric acid piperazine salt obtained by the method of heat-condensing diortrinate monomelamine may be used, and the pyrophosphate piperazine obtained by these methods may be used. Salts and piperazine polyphosphate salts are preferred.
- a commercially available product can be used as the phosphate.
- Examples of commercially available products include "ADEKA FP-2100J”, “ADEKA STABP FP-2200S”, “ADEKA STA FP-2500S”, “FCP-796” by Suzuhiro Chemical, and "EXOLIT AP422" by Clariant Japan.
- EXOLIT AP462 can be mentioned.
- phosphoric acid esters examples include aromatic phosphoric acid esters, aliphatic phosphoric acid esters, and oligomers or polymers obtained from the aromatic phosphoric acid esters and the aliphatic phosphoric acid esters.
- Resolsinol 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.
- a commercially available product can be used as the phosphoric acid ester.
- Examples of commercially available products include "ADEKA STAB FP-600” and “ADEKA STAB FP-800” manufactured by ADEKA.
- 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 ), and copper oxide. , Nickel oxide, tin oxide, aluminum oxide, calcium aluminate and the like. As the metal oxide, zinc oxide, magnesium oxide, or calcium oxide is preferable, and zinc oxide is more preferable.
- the metal oxide may be surface-treated.
- Commercially available zinc oxide includes type 2 zinc oxide manufactured by Shodo Chemical Industry Co., Ltd., type 1 zinc oxide manufactured by Mitsui Metal Mining Co., Ltd., partially coated zinc oxide manufactured by Mitsui Metal Mining Co., Ltd., and Nanofine 50 (average grain). Examples thereof include ultrafine zinc oxide having a diameter of 0.02 ⁇ m: manufactured by Sakai Chemical Industry Co., Ltd. and Nanofine K (an ultrafine zinc oxide coated with zinc silicate having an average particle size of 0.02 ⁇ m: manufactured by Sakai Chemical Industry Co., Ltd.).
- a polyhydric alcohol compound is preferable because it has low water solubility and low hygroscopicity, pentaerythritol, dipentaerythritol, tripentaerythritol, or polypentaerythritol is more preferable, and pentaerythritol is further preferable. ..
- the content of the flame retardant (B) in the polypropylene-based resin composition is preferably 5% by weight or more, more preferably 10% by weight or more, still more preferably 15% by weight, with the total amount of the polypropylene-based resin composition being 100% by weight. % Or more, preferably 50% by weight or less, more preferably 45% by weight or less, still more preferably 40% by weight or less, and preferably 5 to 50% by weight or less.
- the content of the flame retardant other than the phosphorus-containing flame retardant that may be contained in the resin composition is 100% by weight, preferably 0 to 30% by weight. , More preferably 0 to 20% by weight, still more preferably 0 to 10% by weight, and may be 0% by weight.
- the aspect ratio of the glass fiber contained in the resin composition can be measured by the following method. 2 g of the resin composition is dissolved in boiling p-xylene for 2 hours to give a xylene insoluble component containing glass fiber. Next, the glass fibers in the xylene insoluble component are observed using a microscope, and the length and diameter of 200 glass fibers are measured. The weight average fiber length and the average fiber diameter for 200 glass fibers are calculated, and the ratio of the weight average fiber length to the average fiber diameter is defined as the aspect ratio of the glass fibers contained in the resin composition.
- Examples thereof include a method of appropriately adjusting the screw rotation speed; the melt flow rate of the polypropylene-based polymer used as a raw material; the length (fiber length) and the fiber diameter of the glass fiber used as a raw material;
- FIG. 1 is a schematic cross-sectional view showing an example of a twin-screw kneading extruder for producing the resin composition of the present embodiment.
- the twin-screw kneading extruder 100 includes a cylinder 101 and a screw 110 arranged inside the cylinder 101.
- the length of the screw 110 from the upstream end 111 of the kneading resin flow direction F1 to the downstream end 112 (that is, the total length of the screw 110) is L.
- the twin-screw kneading extruder 100 includes a main hopper 130 and a side feeder 140 that supply raw materials into the cylinder 101.
- the main hopper 130 is attached to the cylinder 101 so that the raw material M1 can be supplied into the cylinder 101 at a position L1 from the end 111 on the upstream side of the screw 110.
- the side feeder 140 is attached to the cylinder 101 so that the glass fiber GF can be supplied into the cylinder 101 at a position L2 from the end 111 on the upstream side of the screw 110.
- the supply position of the glass fiber is preferably adjusted so that L2 / L is in the range of 0.3 to 0.9.
- the components of the resin composition other than the glass fiber are supplied into the cylinder 101 at a distance L1 from the position of the end 111 on the upstream side of the screw 110.
- L1 is preferably 0 or more and less than 0.3.
- the aspect ratio and fiber length can be increased.
- the temperature of the extruder is preferably 180 ° C. or higher, more preferably 190 ° C. or higher, still more preferably 200 ° C. or higher, and preferably 250 ° C. or lower.
- the glass fiber may be treated with a sizing agent and / or a surface treating agent.
- the glass fiber is preferably surface-treated with a surface-treating agent from the viewpoint of improving the dispersibility in the polypropylene-based polymer (A).
- surface treatment agents include organic silane coupling agents, titanate coupling agents, aluminate coupling agents, zirconate coupling agents, silicone compounds, higher fatty acids, fatty acid metal salts, and fatty acid esters.
- titanate coupling agents examples include isopropyltriisostearoyl titanate, isopropyltris (dioctylpyrophosphate) titanate, and isopropyltri (N-aminoethyl) titanate.
- higher fatty acids examples include oleic acid, capric acid, lauric acid, palmitic acid, stearic acid, montanic acid, linoleic acid, loginic 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). .. Of these, calcium stearate, aluminum stearate, calcium montanate, and sodium montanate are preferred.
- the amount of the surface treatment agent used is not particularly limited, and is preferably 0.01 parts by weight to 5 parts by weight, more preferably 0.1 parts by weight to 3 parts by weight, based on 100 parts by weight of the glass fiber.
- glass fiber which is a so-called chopped strand obtained by cutting the glass strand may be used. From the viewpoint of further enhancing the effect of improving the rigidity and the effect of improving the impact strength of the molded product containing the polypropylene-based resin composition, it is preferable to use glass fiber which is a chopped strand.
- a resin pellet containing glass fiber (glass fiber-containing resin pellet) may be used.
- the length of the glass fiber (fiber length) is usually substantially the same as the length of the resin pellet in the extrusion direction.
- the glass fiber-containing resin pellets can be produced by any method.
- glass fiber-containing resin pellets can be produced by a pultrusion method.
- the pultrusion method is a method in which a bundle of glass fibers is impregnated by melt-extruding a resin from a resin extruder while drawing out a plurality of continuous glass fibers to integrate the bundles of the plurality of glass fibers. ..
- a bundle of glass fibers impregnated with resin is usually cooled and cut with a pelletizer to obtain glass fiber-containing resin pellets.
- the content of glass fiber in the glass fiber-containing resin pellet is preferably 50 to 99.9% by weight.
- a commercially available product can be used as the glass fiber.
- the polypropylene-based resin composition of the present embodiment may contain an acid-modified polyolefin-based polymer (D) in addition to the polypropylene-based polymer (A), the flame retardant (B), and the glass fiber (C). ..
- the acid-modified polyolefin-based polymer means a polymer obtained by modifying a polyolefin-based polymer with an unsaturated carboxylic acid and / or an unsaturated carboxylic acid derivative.
- the acid-modified polyolefin-based polymer include an acid-modified polyethylene-based polymer and an acid-modified polypropylene-based polymer.
- the acid-modified polyethylene-based polymer means a polymer obtained by modifying a polyethylene-based polymer with an unsaturated carboxylic acid and / or an unsaturated carboxylic acid derivative.
- the acid-modified polypropylene-based polymer means a polymer obtained by modifying a polypropylene-based polymer with an unsaturated carboxylic acid and / or an unsaturated carboxylic acid derivative.
- the modified polyolefin-based polymer is a homopolymer of one kind of olefin or a copolymer of two or more kinds of olefins.
- Examples of the modified polyolefin-based polymer include polyethylene-based polymers and polypropylene-based polymers.
- the modified polyethylene-based polymer is a polymer containing ethylene units in an amount of more than 50% by weight based on all the constituent units of the polymer. The ethylene unit in the polyethylene-based polymer is usually 100% by weight or less.
- the polypropylene-based polymer to be modified is a polymer containing more than 50% by weight of propylene units with respect to all the constituent units of the polymer.
- the propylene unit in the polypropylene-based polymer is usually 100% by weight or less.
- Examples of the polypropylene-based polymer to be acid-modified include the example shown as the polypropylene-based polymer (A) and a preferable example.
- the acid-modified polypropylene-based polymer is usually a polymer having a partial structure of the polypropylene-based polymer and a partial structure derived from an unsaturated carboxylic acid and / or an unsaturated carboxylic acid derivative.
- (C) A block obtained by homopolymerizing propylene and then copolymerizing one or more monomers selected from the group consisting of ethylene and ⁇ -olefin having 4 or more carbon atoms.
- the polymer include a modified polypropylene-based polymer obtained by graft-polymerizing an unsaturated carboxylic acid and / or an unsaturated carboxylic acid derivative.
- Maleic acid monoethyl ester, maleic acid diethyl ester, fumaric acid monomethyl ester, fumaric acid dimethyl ester, acrylamide, methacrylic acid, maleic acid monoamide, maleic acid diamide, fumaric acid monoamide, maleimide, N-butylmaleimide, and sodium methacrylate Can be mentioned.
- Maleic acid and acrylic acid are preferable as the unsaturated carboxylic acid, and maleic anhydride and 2-hydroxyethyl methacrylate are preferable as the unsaturated carboxylic acid derivative.
- the polymer of (b) and the polymer of (c) are preferable.
- the acid-modified polypropylene-based polymer is a modified polyolefin-based polymer obtained by graft-polymerizing maleic anhydride on a polyolefin-based polymer containing more than 50% by weight of propylene units in all the constituent units. Is preferable.
- the total content of the unsaturated carboxylic acid unit and the unsaturated carboxylic acid derivative unit in the acid-modified polyolefin-based polymer is the total content of the acid-modified polyolefin-based polymer from the viewpoint of the rigidity and hardness of the molded product obtained from the resin composition.
- the amount is 100% by weight, preferably 0.1% by weight to 20% by weight, and more preferably 0.1% by weight to 10% by weight.
- the acid-modified polyolefin-based polymer contains only one of the unsaturated carboxylic acid unit and the unsaturated carboxylic acid derivative unit, the total content is the content of the one type unit. means.
- the value calculated by quantifying the absorption based on the unsaturated carboxylic acid and the unsaturated carboxylic acid derivative by the infrared absorption spectrum or the NMR spectrum is used. Use.
- the "graft efficiency of an acid-modified polyolefin-based polymer” means "an unsaturated carboxylic acid and / or an unsaturated carboxylic acid derivative chemically bonded to the polymer contained in the acid-modified polyolefin-based polymer".
- the amount of unsaturated carboxylic acid and / or unsaturated carboxylic acid derivative chemically bonded to the polymer relative to the total amount of unsaturated carboxylic acid and / or unsaturated carboxylic acid derivative that is not chemically bonded to the polymer. It means "ratio".
- the graft efficiency in the graft polymerization of the unsaturated carboxylic acid and / or the unsaturated carboxylic acid derivative can be determined by the following procedures (1) to (9).
- the purified acid-modified polyolefin-based polymer is hot-pressed to prepare a film having a thickness of 100 ⁇ m; (6) Measure the infrared absorption spectrum of the film; (7) From the infrared absorption spectrum, the absorption based on the unsaturated carboxylic acid and / or the unsaturated carboxylic acid derivative was quantified, and the unsaturated carboxylic acid and / or the unsaturated carboxylic acid reacted with the polyolefin polymer in the acid-modified polyolefin polymer. The content (X1) of the unsaturated carboxylic acid derivative is calculated.
- the unpurified acid-modified polyolefin-based polymer is subjected to the above steps (5) to (6), and from the infrared absorption spectrum thereof, the unpurified acid-modified polyolefin-based polymer is contained.
- the content (X2) of the unsaturated carboxylic acid and / or the unsaturated carboxylic acid derivative is calculated (X2 is the content of the unsaturated carboxylic acid and / or the unsaturated carboxylic acid derivative that has reacted with the polypropylene-based polymer (X1).
- the MFR of the acid-modified polypropylene-based polymer is preferably 5 to 400 g / 10 minutes, more preferably 10 to 200 g / 10 minutes, and particularly preferably 20 to 200 g, from the viewpoint of mechanical strength and production stability. / 10 minutes.
- the MFR is a value measured at 230 ° C. and a 2.16 kgf load according to JIS K7210-1: 2014 and K7210-2: 2014.
- the ⁇ -olefin having 4 to 10 carbon atoms constituting the random copolymer which is an elastomer is the same as the ⁇ -olefin having 4 to 10 carbon atoms which can form the polypropylene-based polymer (A).
- Examples thereof include ⁇ -olefins, and specific examples thereof include ⁇ -olefins having a chain structure such as 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, and 1-decene.
- ⁇ -olefins having a cyclic structure such as vinylcyclopropane and vinylcyclobutane, preferably 1-butene, 1-hexene and 1-octene.
- Examples of the random copolymer which is an elastomer include ethylene-1-butene random copolymer, ethylene-1-hexene random copolymer, ethylene-1-octene random copolymer, and ethylene-1-decene random copolymer.
- Examples include polymers, ethylene- (3-methyl-1-butene) random copolymers, and polymers of ethylene with ⁇ -olefins having a cyclic structure.
- the content of the ⁇ -olefin in the random copolymer is preferably 1 to 49% by weight, more preferably 5 to 49% by weight, further preferably 100% by weight, based on the weight of the random copolymer. Is 24-49% by weight.
- the density of the random copolymer is preferably 0.850 to 0.890 g / cm 3 , more preferably 0.850 to 0. It is 880 g / cm 3 , more preferably 0.855 to 0.867 g / cm 3 .
- the random copolymer which is an elastomer, can be produced by polymerizing a monomer using a polymerization catalyst.
- the polymerization catalyst include the catalysts mentioned as examples of the polymerization catalyst for producing the polypropylene-based polymer.
- random copolymer a commercially available product may be used.
- examples of commercially available products such as the random copolymer which is an elastomer include Dow Chemical Japan's Engage (registered trademark), Mitsui Chemicals' Toughmer (registered trademark), Prime Polymer's Neozex (registered trademark), and Ult.
- Examples thereof include ZEX (registered trademark), Excellen FX (registered trademark) manufactured by Sumitomo Chemicals, Sumikasen (registered trademark), and Esplen SPO (registered trademark).
- the content of the elastomer in the resin composition is preferably 0 to 30% by weight, more preferably 0 to 10% by weight, based on 100% by weight of the resin composition. In one embodiment, the content of the elastomer in the resin composition may be 5 to 30% by weight.
- the polypropylene-based resin composition of the present embodiment has a melt flow rate of preferably 0.1 g / 10 minutes or more, more preferably 1 g / 10 minutes or more, measured under the conditions of 230 ° C. and a load of 2.16 kgf. It is preferably 400 g / 10 minutes or less, more preferably 300 g / 10 minutes or less, and further preferably 200 g / 10 minutes or less.
- MFR of the resin composition is not more than the upper limit of the above range, the flame retardant performance of the resin composition can be effectively improved, and when it is not more than the lower limit of the above range, the molded product containing the resin composition is contained. Weld strength can be good.
- the polypropylene-based resin composition of the present embodiment can produce a molded product (particularly, an injection molded product) having excellent flame retardancy and a good appearance.
- the molded body include an injection molded body, an extrusion molded body, a compression molded body, a deformed molded body, a vacuum molded body, a sheet molded body, a roll molded body, a hot press molded body, a foam molded body, an injection press molded body, and a blow.
- examples thereof include a molded product and a gas injection molded product.
- the dimensions of the molded product are not particularly limited, but for example, the outer dimensions are 0.5 to 2 m in length, 0.5 to 2 m in width, and 1 to 10 mm in thickness.
- the shape of the molded body may be, for example, a plate shape or a hollow shape.
- the polypropylene-based resin composition of the present embodiment can be suitably used as a material for various members (for example, automobile interior / exterior parts, engine room interior parts, two-wheeled vehicle parts, electrical product parts, various containers, furniture).
- interior and exterior components for automobiles include instrument panels, door trims, pillars, side protectors, console boxes, column covers, bumpers, fenders, and wheel covers.
- Examples of parts in the engine room of an automobile include a battery case and an engine cover.
- motorcycle parts include cowlings and muffler covers.
- the polypropylene-based resin composition of the present embodiment can be produced by any method.
- the polypropylene-based resin composition is a polypropylene-based polymer (A), a flame retardant (B), a glass fiber (C), and optionally in a twin-screw kneading extruder equipped with a cylinder and two screws. Any component to be added can be produced by kneading.
- the raw material (1) containing the polypropylene-based polymer (A) and the flame retardant (B) is placed in the cylinder of the twin-screw kneading extruder at a distance L1 from the upstream end of the two screws.
- the glass fiber (C) is supplied into the cylinder at a position L2 from the end on the upstream side of the two screws.
- L1 / L is preferably in the range of 0 or more and less than 0.3
- L2 / L is preferably in the range of 0.3 to 0.9.
- L2 / L is more preferably 0.5 or more, further preferably 0.6 or more, and more preferably 0.5 to 0.9. More preferably, it is 0.6 to 0.9.
- L2 / L is reduced, the aspect ratio of the glass fiber contained in the resin composition can be reduced, and when L2 / L is increased, the aspect ratio can be increased.
- the raw material (1) may contain, as an optional component, a molecular weight adjusting agent for adjusting the molecular weight of the polypropylene-based polymer.
- a molecular weight adjusting agent for adjusting the molecular weight of the polypropylene-based polymer.
- molecular weight modifiers include organic peroxides.
- the molecular weight adjusting agent may be contained in the raw material (1) in the form of a masterbatch diluted with an arbitrary resin.
- the molded product according to the embodiment of the present invention contains the polypropylene-based resin composition.
- the molded product according to the present embodiment is made of a polypropylene-based resin composition, and can be formed by molding the polypropylene-based resin composition. Since the molded product according to the present embodiment contains the polypropylene-based resin composition, it has excellent flame retardancy and a good appearance.
- polypropylene-based resin compositions that can be contained in the molded product and preferable examples are described in the above item [1.
- Polypropylene-based resin composition] is the same as the example described and the preferred example.
- the molding method is arbitrary, and examples thereof include an injection molding method.
- the injection molding method include an injection foam molding method, a supercritical injection foam molding method, and an ultrahigh speed injection in addition to a general injection molding method.
- Examples include a 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 / outsert molding method.
- As the molded body an injection molded body molded by an injection molding method is preferable.
- the dimensions of the molded product are not particularly limited, but for example, the outer dimensions are 0.5 to 2 m in length, 0.5 to 2 m in width, and 1 to 10 mm in thickness.
- the shape of the molded body may be, for example, a plate shape or a hollow shape.
- the molded product of the present embodiment can be suitably used for the same purpose as the example of the use described in the use of the polypropylene-based resin composition.
- Li is the length of the glass fiber (fiber length)
- qi is the number of glass fibers having the fiber length Li.
- the resin composition was injection molded using an injection molding machine (“IS100EN” manufactured by Toshiba Machine Co., Ltd.) to prepare a test flat plate having a size of 160 mm (length) ⁇ 160 mm (horizontal) ⁇ 2.0 mm (thickness).
- the molding conditions were a molding temperature of 220 ° C. and a mold cooling temperature of 50 ° C.
- the appearance of the obtained test plate was visually observed and evaluated according to the following criteria.
- Defective (x) The embossed glass fiber is conspicuous on the surface of the test plate.
- the resin composition is supplied to an injection molding machine: "SYCAP110" manufactured by Sumitomo Heavy Industries, Ltd., and injection molding is performed under the conditions of a molding temperature of 230 ° C. and a mold cooling temperature of 50 ° C., 127 mm (length) x 13 mm (width). ) X 1.6 mm (thickness) test piece was prepared. Using the obtained test piece, the flame retardancy of the test piece was evaluated according to the UL94-V standard. V-0 is superior to V-1 and V-1 is superior to V-2 in terms of flame retardancy.
- the resin composition is supplied to an injection molding machine: "IS100EN” manufactured by Toshiba Machine Co., Ltd., and injection molding is performed under the conditions of a molding temperature of 220 ° C. and a mold cooling temperature of 50 ° C., and 160 mm (vertical) x 160 mm (horizontal) x A 2.0 mm (thickness) test plate was prepared. The obtained test plate was used to perform a plaque test based on the standard UL94-5V.
- the obtained test plate having a thickness of 2.0 mm was cut into 127 mm (length) ⁇ 13 mm (width) ⁇ 2.0 mm (thickness) to obtain a test piece, and a bar was obtained based on the standard UL94-5V. A test was conducted. If the criteria for plaque and bar tests were met, the rating was 5VA.
- Propylene homopolymers (A-1) to (A-3) as polypropylene-based polymers are vaporized from propylene using a polymerization catalyst obtained by the method described in Example 1 of JP-A-2004-182981. Manufactured by the phase polymerization method. The production conditions were such that the polymers (A-1) to (A-3) each had the following physical properties.
- a flame retardant containing melamine phosphate and piperidin phosphate as main components product name: ADEKA STAB FP-2200S, manufactured by ADEKA was used.
- Component (D): Maleic anhydride-modified polypropylene-based polymer) 100 parts by weight of propylene polymer powder (extreme viscosity number [ ⁇ ] 3.0 dL / g, ethylene unit content 0.2% by weight), 1.0 part by weight of maleic anhydride, di- (tert-butylper) Oxy) Diisopropylbenzene (product name: Perbutyl P, manufactured by Nippon Oil & Fats Co., Ltd.) is 0.14 parts by weight, disetylperoxydicarbonate (product name: Percadox 24FL, manufactured by Chemicals Axo) is 0.05 parts by weight, 0.05 parts by weight of calcium stearate (product name: AR-2, manufactured by Sakai Chemical Industry Co., Ltd.), pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate as an antioxidant ] (Product name: benzen
- the obtained maleic anhydride-modified polypropylene polymer as the acid-modified polypropylene-based polymer has an MFR (230 ° C., load 2.16 kgf) of 170 g / 10 minutes and a content of maleic anhydride unit of 0.32 (weight). %)Met.
- Example 1 Manufacturing of polypropylene resin composition
- the component (A) polypropylene polymer
- the component (D) acid-modified polypropylene-based polymer
- the component (B) phosphorus-containing flame retardant
- Calcium stearate (Product name: Calcium stearate S, manufactured by Nippon Oil & Fat Co., Ltd.) 0.05 parts by weight, 3,9-bis [2- (3- (3-tert-butyl-4-hydroxy-5-) as an antioxidant Methylphenyl) propionyloxy) -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane (product name: PolymerGA80, manufactured by Sumitomo Chemical Co., Ltd.) 0.1 part by weight, 3 , 9-bis (2,4-di-tert-butylphenoxy) -2,4,8,10-tetraoxaspiro [5.5] undecane (product name: Songnox6260, manufactured by SONGWON) 0.2 parts by weight, And dimyristyl-3,3-thiodipropionate (product name: SumilizerTPM, manufactured by Sumitomo Chemical Co., Ltd.) 0.2 parts by weight
- the component (C) (glass fiber) having the composition shown in Table 1-1 is supplied to the melt-kneaded kneaded material from a side feeder provided in the middle of the twin-screw kneading extruder and further kneaded to further knead the die.
- the pellet was dried in a hot air dryer at 100 ° C.
- Example 2 Component (A) (polypropylene polymer), component (D) (acid-modified polypropylene polymer), component (B) (phosphorus-containing flame retardant), component (C) (glass) of the formulations shown in Table 1-1. Fiber) was used. Further, the total weight of the component (A), the component (D), the component (B), and the component (C) is 100 parts by weight, and 0.58 parts by weight of the organic peroxide masterbatch (product name: CH). -11, manufactured by Kayaku Akzo Corporation, containing 8% of organic peroxide component) was used. Except for the above items, the same procedure as in Example 1 was carried out to obtain pellets of the polypropylene-based resin composition to be evaluated. The obtained pellets of the polypropylene-based resin composition were molded by the above-mentioned method to obtain a test piece or a test plate, and evaluated. The evaluation results are shown in Table 2-1.
- Examples 3 to 8 The components (A) (polypropylene-based polymer), (D) component (acid-modified polypropylene-based polymer), (B) component (phosphorus-containing flame retardant), and ( C) Component (glass fiber) was used. In addition, an organic peroxide masterbatch (product name: CH-11, manufactured by Kayaku Akzo Corporation, containing 8% of organic peroxide component) was not used. Except for the above items, the same procedure as in Example 1 was carried out to obtain pellets of the polypropylene-based resin composition to be evaluated. The obtained pellets of the polypropylene-based resin composition were molded by the above-mentioned method to obtain a test piece or a test plate, and evaluated. The evaluation results are shown in Tables 2-1 to 2-2.
- Example 9 Component (A) (polypropylene polymer), component (D) (acid-modified polypropylene polymer), component (B) (phosphorus-containing flame retardant), component (C) (glass) of the formulations shown in Table 1-2. Fiber) was used. Further, the total weight of the component (A), the component (D), the component (B), and the component (C) is 100 parts by weight, and 0.30 parts by weight of the organic peroxide masterbatch (product name: CH). -11, manufactured by Kayaku Akzo Corporation, containing 8% of organic peroxide component) was used. Except for the above items, the same procedure as in Example 1 was carried out to obtain pellets of the polypropylene-based resin composition to be evaluated. The obtained pellets of the polypropylene-based resin composition were molded by the above-mentioned method to obtain a test piece or a test plate, and evaluated. The evaluation results are shown in Table 2-2.
- Component (A) (polypropylene polymer), component (D) (acid-modified polypropylene polymer), component (B) (phosphorus-containing flame retardant), component (C) (glass) of the formulations shown in Table 1-3.
- the total weight of the fiber) and the components (A), (D), (B), and (C) is 100 parts by weight, and calcium stearate (product name: calcium stearate S, as a neutralizing agent) is used as a neutralizing agent.
- the melt-kneaded kneaded product was extruded from a die, the extruded product was passed through a cold water tank to form strands, and then the strands were cut with a strand cutter to obtain pellets.
- the pellet was dried in a hot air dryer at 100 ° C. for 2 hours to obtain a pellet of a polypropylene-based resin composition to be evaluated.
- the obtained pellets of the polypropylene-based resin composition were molded by the above-mentioned method to obtain a test piece or a test plate, and evaluated. The evaluation results are shown in Table 2-3.
- Component (A) polypropylene polymer
- component (D) acid-modified polypropylene polymer
- component (B) phosphorus-containing flame retardant
- component (C) glass of the formulations shown in Table 1-3. Fiber
- the total weight of the component (A), the component (D), the component (B), and the component (C) is 100 parts by weight, and 0.30 parts by weight of the organic peroxide masterbatch (product name: CH-11).
- the organic peroxide masterbatch product name: CH-11.
- Example 2 Except for the above items, the same procedure as in Example 1 was carried out to obtain pellets of the polypropylene-based resin composition to be evaluated.
- the obtained pellets of the polypropylene-based resin composition were molded by the above-mentioned method to obtain a test piece or a test plate, and evaluated.
- the evaluation results are shown in Table 2-3.
- PP Polypropylene-based polymer
- A-1 (MFR: 14) Propylene homopolymer (A-1) "A-2 (MFR: 120)”: Propylene homopolymer (A-2) "A-3 (MFR: 240)”: Propylene homopolymer (A-3)
- Acid-modified PP Acid-modified polypropylene-based polymer
- MPA Maleic anhydride-modified polypropylene-based polymer
- FP2200S Flame retardant (Product name: ADEKA STAB FP-2200S, manufactured by ADEKA)
- GF Glass fiber
- C-1 Glass fiber (C-1) (chopped strand 1)
- C-2 Glass fiber (C-2) (milled fiber)
- C-3 Glass fiber (C-3) (chopped strand 2)
- CH-11 Organic peroxide masterbatch
- CH-11 Organic peroxide masterbatch
- each of the components (A) to (D) is a numerical value expressing the total content of the components (A) to (D) as 100% by weight.
- composition and evaluation results of resin composition The composition and evaluation results of the resin composition are shown in the table below.
- the column where the evaluation is not described in the item of the combustion test (UL94 5V) indicates that the evaluation of the combustion test (UL94 5V) has not been performed.
- the abbreviations in the table have the following meanings. "1.6 mmt": Thickness 1.6 mm "2.0 mmt”: Thickness 2.0 mm
- the molded product formed from the polypropylene-based resin composition containing the glass fiber having an aspect ratio of 20 to 60 according to Examples 1 to 9 has an excellent evaluation of flame retardancy according to the UL94-V standard.
- the molded product formed from the polypropylene-based resin composition containing the glass fiber having an aspect ratio of less than 20 according to Comparative Examples 1 and 2 is inferior in the evaluation of flammability according to the UL94-V standard.
- the molded product formed from the polypropylene-based resin composition containing glass fibers having an aspect ratio of more than 60 according to Comparative Example 3 has a poor appearance.
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
このような難燃性を有するポリオレフィン系樹脂組成物として、例えば、ガラス繊維及び難燃剤を含むポリオレフィン系樹脂組成物が知られている(特許文献1)。
そこで、外観を損なうことなく、かつ難燃性に優れた成形体を製造しうる、ポリプロピレン系樹脂組成物が求められている。
[2] ガラス繊維(C)の長さが、200~600μmである、[1]に記載のポリプロピレン系樹脂組成物。
[3] さらに酸変性ポリオレフィン系重合体(D)を含む、[1]又は[2]に記載のポリプロピレン系樹脂組成物。
[4] ポリプロピレン系樹脂組成物の全量を100重量%としたとき、
ポリプロピレン系重合体(A)の含有量が30~70重量%であり、
難燃剤(B)の含有量が5~50重量%であり、
ガラス繊維(C)の含有量が5~40重量%である、
[1]~[3]のいずれか一項に記載のポリプロピレン系樹脂組成物。
[5] [1]~[4]のいずれか一項に記載のポリプロピレン系樹脂組成物を含む、成形体。
[6] 外寸が、縦0.5~2m、横0.5~2m、及び厚さ1~10mmである、[5]に記載の成形体。
[8] [1]~[5]のいずれか一項に記載のポリプロピレン系樹脂組成物の製造方法であって、
ポリプロピレン系重合体(A)と難燃剤(B)とを含む原料(1)と、ガラス繊維(C)とを、シリンダと、前記シリンダ内に配置された、全長がLである二本のスクリューとを備える二軸混練押出機中で混練してポリプロピレン系樹脂組成物を得る工程を含み、
前記原料(1)を、前記シリンダ内に、前記二本のスクリューの上流側における端の位置からの距離L1で供給し、前記ガラス繊維(C)を、前記シリンダ内に、前記二本のスクリューの上流側における端からの距離L2の位置で供給し、L1/Lが0以上0.3未満の範囲であり、L2/Lが0.3~0.9の範囲である、ポリプロピレン系樹脂組成物の製造方法。
ウベローデ型粘度計を用いて、複数の濃度について還元粘度を測定し、還元粘度を濃度に対しプロットし、濃度をゼロに外挿する「外挿法」により極限粘度数を求める。より具体的には、「高分子溶液、高分子実験学11」(1982年共立出版株式会社刊)第491頁に記載の方法を用い、濃度0.1g/dL、0.2g/dL及び0.5g/dLの3点について還元粘度を測定し、還元粘度を濃度に対しプロットし、濃度をゼロに外挿する方法により求める。
本発明の一実施形態に係るポリプロピレン系樹脂組成物は、ポリプロピレン系重合体(A)と、難燃剤(B)と、アスペクト比が20~60であるガラス繊維(C)とを含む。 本実施形態のポリプロプレン系樹脂組成物を成形物は、難燃性に優れ、かつ外観が良好である。以下、本実施形態のポリプロピレン系樹脂組成物を、単に樹脂組成物ともいう。
ポリプロピレン系重合体とは、プロピレン単位を、重合体の全構成単位に対して50重量%より多く含有する重合体である。ポリプロピレン系重合体におけるプロピレン単位は、通常100重量%以下である。
ポリプロピレン系重合体の例としては、プロピレン単独重合体;及び、プロピレンと、これと共重合しうる他のモノマーとの共重合体が挙げられる。前記の共重合体は、ランダム共重合体であってもよく、ブロック共重合体であってもよい。
ポリプロピレン系樹脂組成物は、一種単独のポリプロピレン系重合体を含んでいてもよく、二種以上のポリプロピレン系重合体を、任意の比率の組み合わせで含んでいてもよい。
一種単独のポリプロピレン系重合体の例としては、プロピレンの単独重合体;及び、プロピレンと、これと共重合しうる他のモノマーとのランダム共重合体(以下、ポリプロピレン系ランダム共重合体ともいう。)が挙げられる。
二種以上のポリプロピレン系重合体の組み合わせの例としては、重量平均分子量等が異なる、二種以上のプロピレン単独重合体の組み合わせ;下記重合体(I)及び重合体(II)の組み合わせが挙げられる。
ポリプロピレン系樹脂組成物は、ポリプロピレン系重合体として、ヘテロファジックプロピレン重合体材料を含んでいてもよい。ここで、ヘテロファジックプロピレン重合体材料とは、二種以上のポリプロピレン系重合体を含み、当該二種以上のポリプロピレン系重合体が相溶せずに、互いに別の相を形成している材料を意味する。
ヘテロファジックプロピレン重合体材料の例としては、下記重合体(I)及び重合体(II)の組み合わせが挙げられる。
ここで、重合体(I)は、プロピレン単位を全構成単位の量に対して80重量%より多く100重量%以下有する重合体であり、重合体(II)は、プロピレン単位と、エチレン単位及び炭素原子数が4個以上のα-オレフィン単位からなる群から選択される少なくとも一種のモノマー単位との共重合体である。重合体(I)は、プロピレン単独重合体であってもよく、プロピレンと他のモノマーとの共重合体であってもよい。重合体(I)及び重合体(II)はそれぞれ、一種単独の重合体であってもよく、二種以上の重合体の組み合わせであってもよい。
プロピレン単独重合体は、樹脂組成物の溶融時の流動性と、樹脂組成物を含む成形体の靱性とを良好にする観点から、極限粘度数[η]が、好ましくは0.1~2dL/gであり、より好ましくは0.5~1.5dL/gであり、更に好ましくは0.7~1.4dL/gである。ここで、極限粘度数[η]は、135℃においてテトラリン中で測定される数値である。
ポリプロピレン系ランダム共重合体の例としては、プロピレン単位とエチレン単位とを含むランダム共重合体(以下、ランダム共重合体(1)ともいう。);プロピレン単位と、炭素原子数が4個以上のα-オレフィン単位とを含むランダム共重合体(以下、ランダム重合体(2)ともいう。);及び、プロピレン単位と、エチレン単位と、炭素原子数が4個以上のα-オレフィン単位とを含むランダム共重合体(以下、ランダム重合体(3)ともいう。)が挙げられる。
ランダム共重合体(2)中の、炭素原子数が4個以上のα-オレフィン単位の含有量は、好ましくは0.1~40重量%、より好ましくは0.1~30重量%、更に好ましくは2~15重量%である。
ランダム共重合体(3)中の、エチレン単位及び炭素原子数が4個以上のα-オレフィン単位の合計含有量は、好ましくは0.1~40重量%、より好ましくは0.1~30重量%、更に好ましくは2~15重量%である。
重合体(I)は、前記のとおり、プロピレン単位を全構成単位の量に対して80重量%より多く100重量%以下有する重合体である。重合体(I)中のプロピレン単位以外のモノマー単位の合計の含有量は、重合体(I)の重量を100重量%として、通常0重量%以上20重量%未満であり、0重量%であってもよく、0.01重量%以上であってもよい。
重合体(I)を構成しうる、炭素原子数が4個以上のα-オレフィンは、好ましくは炭素原子数が4~10個のα-オレフィンであり、より好ましくは1-ブテン、1-ヘキセン及び1-オクテンであり、更に好ましくは1-ブテンである。
プロピレン単独重合体と(プロピレン-エチレン)共重合体との組み合わせ;プロピレン単独重合体と(プロピレン-エチレン-1-ブテン)共重合体との組み合わせ;プロピレン単独重合体と(プロピレン-エチレン-1-ヘキセン)共重合体との組み合わせ;プロピレン単独重合体と(プロピレン-エチレン-1-オクテン)共重合体との組み合わせ;プロピレン単独重合体と(プロピレン-1-ブテン)共重合体との組み合わせ;プロピレン単独重合体と(プロピレン-1-ヘキセン)共重合体との組み合わせ;プロピレン単独重合体と(プロピレン-1-オクテン)共重合体との組み合わせ;及び、プロピレン単独重合体と(プロピレン-1-デセン)共重合体との組み合わせ。
(プロピレン-エチレン)共重合体と(プロピレン-エチレン)共重合体との組み合わせ;(プロピレン-エチレン)共重合体と(プロピレン-エチレン-1-ブテン)共重合体との組み合わせ;(プロピレン-エチレン)共重合体と(プロピレン-エチレン-1-ヘキセン)共重合体との組み合わせ;(プロピレン-エチレン)共重合体と(プロピレン-エチレン-1-オクテン)共重合体との組み合わせ;(プロピレン-エチレン)共重合体と(プロピレン-エチレン-1-デセン)共重合体との組み合わせ;(プロピレン-エチレン)共重合体と(プロピレン-1-ブテン)共重合体との組み合わせ;(プロピレン-エチレン)共重合体と(プロピレン-1-ヘキセン)共重合体との組み合わせ;(プロピレン-エチレン)共重合体と(プロピレン-1-オクテン)共重合体との組み合わせ;(プロピレン-エチレン)共重合体と(プロピレン-1-デセン)共重合体との組み合わせ;(プロピレン-1-ブテン)共重合体と(プロピレン-エチレン)共重合体との組み合わせ;(プロピレン-1-ブテン)共重合体と(プロピレン-エチレン-1-ブテン)共重合体との組み合わせ;(プロピレン-1-ブテン)共重合体と(プロピレン-エチレン-1-ヘキセン)共重合体との組み合わせ;(プロピレン-1-ブテン)共重合体と(プロピレン-エチレン-1-オクテン)共重合体との組み合わせ;(プロピレン-1-ブテン)共重合体と(プロピレン-エチレン-1-デセン)共重合体との組み合わせ;(プロピレン-1-ブテン)共重合体と(プロピレン-1-ブテン)共重合体との組み合わせ;(プロピレン-1-ブテン)共重合体と(プロピレン-1-ヘキセン)共重合体との組み合わせ;(プロピレン-1-ブテン)共重合体と(プロピレン-1-オクテン)共重合体との組み合わせ;(プロピレン-1-ブテン)共重合体と(プロピレン-1-デセン)共重合体との組み合わせ;(プロピレン-1-ヘキセン)共重合体と(プロピレン-1-ヘキセン)共重合体との組み合わせ;(プロピレン-1-ヘキセン)共重合体と(プロピレン-1-オクテン)共重合体との組み合わせ;(プロピレン-1-ヘキセン)共重合体と(プロピレン-1-デセン)共重合体との組み合わせ;(プロピレン-1-オクテン)共重合体と(プロピレン-1-オクテン)共重合体との組み合わせ;及び、(プロピレン-1-オクテン)共重合体と(プロピレン-1-デセン)共重合体との組み合わせ。
[η]Total:最終重合体の極限粘度数(単位:dL/g)
[η]I:重合体(I)の極限粘度数(単位:dL/g)
XI:最終重合体に対する重合体(I)の重量比
XII:最終重合体に対する重合体(II)の重量比
なお、XI及びXIIは重合時の物質収支から求める。
XII=1-(ΔHf)T/(ΔHf)P
(ΔHf)T:最終重合体(重合体(I)及び重合体(II))の融解熱量(単位:cal/g)
(ΔHf)P:重合体(I)の融解熱量(単位:cal/g)
ポリプロピレン系樹脂組成物中のポリプロピレン系重合体(A)の含有量は、ポリプロピレン系樹脂組成物の全量を100重量%として、好ましくは30重量%以上、より好ましくは35重量%以上、更に好ましくは40重量%以上であり、好ましくは70重量%以下、より好ましくは65重量%以下、更に好ましくは60重量%以下であり、好ましくは30~70重量%以下である。
樹脂組成物は、難燃剤を含む。樹脂組成物は、難燃剤を一種単独で含んでいてもよく、二種以上の任意の比率の組み合わせで含んでいてもよい。
ピロリン酸メラミン塩及びポリリン酸メラミン塩として、オルトリン酸一メラミンを加熱縮合させる方法により得られたピロリン酸メラミン塩及びポリリン酸メラミン塩を用いてもよく、これらの方法により得られたピロリン酸メラミン塩及びポリリン酸メラミン塩が好ましい。
ピロリン酸ピペラジン塩及びポリリン酸ピペラジン塩として、二オルトリン酸一メラミンを加熱縮合させる方法により得られたピロリン酸ピペラジン塩及びポリリン酸ピペラジン塩を用いてもよく、これらの方法により得られたピロリン酸ピペラジン塩及びポリリン酸ピペラジン塩が好ましい。
ポリプロピレン系樹脂組成物中の難燃剤(B)の含有量は、ポリプロピレン系樹脂組成物の全量を100重量%として、好ましくは5重量%以上、より好ましくは10重量%以上、更に好ましくは15重量%以上であり、好ましくは50重量%以下、より好ましくは45重量%以下、更に好ましくは40重量%以下であり、好ましくは5~50重量%以下である。
樹脂組成物に含まれるガラス繊維(C)は、通常、アスペクト比が20~60である。 アスペクト比は、好ましくは25以上、より好ましくは30以上であり、好ましくは58以下、より好ましくは55以下である。
樹脂組成物2gを、沸騰しているp-キシレン中で2時間溶解して、ガラス繊維を含む、キシレン不溶成分を得る。次いで、キシレン不溶成分中のガラス繊維を、マイクロスコープを用いて観察し、ガラス繊維200本の長さ及び径を測定する。ガラス繊維200本についての重量平均繊維長及び平均繊維径を算出し、重量平均繊維長の平均繊維径に対する比を、樹脂組成物に含まれるガラス繊維のアスペクト比とする。
図1は、本実施形態の樹脂組成物を製造するための二軸混練押出機の一例を示す、模式的な断面図である。
二軸混練押出機100は、シリンダ101と、シリンダ101の内部に配置されたスクリュー110とを備える。スクリュー110は、混練する樹脂流れの方向F1の上流側の端111から、下流側の端112までの長さ(すなわち、スクリュー110の全長)が、Lである。
二軸混練押出機100は、原料をシリンダ101内に供給するメインホッパー130及びサイドフィーダー140とを備える。メインホッパー130は、原料M1を、スクリュー110の上流側における端111から距離L1の位置で、シリンダ101内に供給できるようにシリンダ101に取り付けられている。また、サイドフィーダー140は、ガラス繊維GFを、スクリュー110の上流側における端111から距離L2の位置で、シリンダ101内に供給できるように、シリンダ101に取り付けられている。
好ましくはL2/Lが0.3~0.9の範囲となるようにガラス繊維の供給位置を調整する。
ここで、通常、ガラス繊維を除く樹脂組成物の成分は、スクリュー110の上流側における端111の位置から距離L1の位置で、シリンダ101内に供給する。L1は、好ましくは0以上0.3未満である。
L2/Lは、より好ましくは0.5以上、更に好ましくは0.6以上であり、より好ましくは0.5~0.9.更に好ましくは0.6~0.9である。通常、L2/Lを小さくすると、樹脂組成物に含まれるガラス繊維のアスペクト比を小さくでき、L2/Lを大きくすると、当該アスペクト比を大きくできる。
ポリプロピレン系樹脂組成物中のガラス繊維(C)の含有量は、ポリプロピレン系樹脂組成物の全量を100重量%として、好ましくは5重量%以上、より好ましくは8重量%以上、更に好ましくは10重量%以上であり、好ましくは40重量%以下、より好ましくは38重量%以下、更に好ましくは35重量%以下であり、好ましくは5~40重量%以下である。
ジルコネートカップリング剤の例としては、テトラ(2,2-ジアリルオキシメチル)ブチル、ジ(トリデシル)ホスファイトジルコネート、及びネオペンチル(ジアリル)オキシトリネオデカノイルジルコネートが挙げられる。
前記シリコーン化合物としては、シリコーンオイル、及びシリコーン樹脂が挙げられる。
集束剤は、ポリプロピレン系重合体(A)との溶融混練の温度において融解するものが好ましく、200℃以下で溶融するものがより好ましい。
例えば、ガラス繊維含有樹脂ペレットは、引抜成形法により製造しうる。引抜成形法とは、通常、複数本の連続したガラス繊維を引き出しながら、樹脂押出機から樹脂を溶融押出してガラス繊維の束に含浸させ、複数本のガラス繊維の束を一体化する方法である。樹脂を含浸させたガラス繊維の束を、通常、冷却し、ペレタイザーにより切断して、ガラス繊維含有樹脂ペレットを得る。
本実施形態のポリプロピレン系樹脂組成物は、ポリプロピレン系重合体(A)、難燃剤(B)、及びガラス繊維(C)に加えて、酸変性ポリオレフィン系重合体(D)を含んでいてもよい。
酸変性ポリオレフィン系重合体の例としては、酸変性ポリエチレン系重合体、及び、酸変性ポリプロピレン系重合体が挙げられる。
酸変性ポリエチレン系重合体とは、ポリエチレン系重合体を、不飽和カルボン酸及び/又は不飽和カルボン酸誘導体で変性して得られる重合体を意味する。
酸変性ポリプロピレン系重合体とは、ポリプロピレン系重合体を、不飽和カルボン酸及び/又は不飽和カルボン酸誘導体で変性して得られる重合体を意味する。
変性されるポリオレフィン系重合体は、1種類のオレフィンの単独重合体または2種類以上のオレフィンの共重合体である。変性されるポリオレフィン系重合体の例としては、ポリエチレン系重合体、及び、ポリプロピレン系重合体が挙げられる。
変性されるポリエチレン系重合体は、エチレン単位を、重合体の全構成単位に対して50重量%より多く含有する重合体であり。ポリエチレン系重合体におけるエチレン単位は、通常100重量%以下である。
(2)キシレン溶液をメタノール1000mlに攪拌しながら滴下して酸変性ポリオレフィン系重合体を再沈殿させる;
(3)再沈殿した酸変性ポリオレフィン系重合体を回収する;
(4)回収された酸変性ポリオレフィン系重合体を80℃にて8時間真空乾燥し、精製された酸変性ポリオレフィン系重合体を得る;
(5)精製された酸変性ポリオレフィン系重合体を熱プレスし、厚さ100μmのフィルムを作製する;
(6)フィルムの赤外吸収スペクトルを測定する;
(7)赤外吸収スペクトルから、不飽和カルボン酸及び/又は不飽和カルボン酸誘導体に基づく吸収を定量し、酸変性ポリオレフィン系重合体中のポリオレフィン系重合体と反応した不飽和カルボン酸及び/又は不飽和カルボン酸誘導体の含有量(X1)を算出する。
(8)別途、精製処理していない酸変性ポリオレフィン系重合体について、前記の手順(5)~(6)を行ない、その赤外吸収スペクトルから、精製処理していない酸変性ポリオレフィン系重合体中の不飽和カルボン酸及び/又は不飽和カルボン酸誘導体の含有量(X2)を算出する(X2は、ポリプロピレン系重合体と反応した不飽和カルボン酸及び/又は不飽和カルボン酸誘導体の含有量(X1)と、ポリオレフィン系重合体と反応していない(つまり、遊離の)不飽和カルボン酸及び/又は不飽和カルボン酸誘導体の含有量との合計である);
(9)式:グラフト効率=X1/X2からグラフト効率を算出する。
本実施形態のポリプロピレン系樹脂組成物は、前記の成分(A)~(C)、任意に含まれる前記成分(D)に加えて、さらに任意成分を含んでいてもよい。
任意成分の例としては、エラストマー、中和剤、酸化防止剤、紫外線吸収剤、滑剤、帯電防止剤、アンチブロッキング剤、加工助剤、有機系過酸化物、着色剤(無機顔料、有機顔料等)、顔料分散剤、発泡剤、発泡核剤、可塑剤、架橋剤、架橋助剤、高輝度化剤、抗菌剤、及び光拡散剤が挙げられる。樹脂組成物は、これらの任意成分を、一種単独で含んでいてもよく、二種以上の任意の比率の組み合わせで含んでいてもよい。
一実施形態において、樹脂組成物中のエラストマーの含有量は、5~30重量%であってもよい。
本実施形態のポリプロピレン系樹脂組成物は、230℃、荷重2.16kgfの条件で測定されるメルトフローレートが、好ましくは0.1g/10分以上、より好ましくは1g/10分以上であり、好ましくは400g/10分以下、より好ましくは300g/10分以下、更に好ましくは200g/10分以下である。樹脂組成物のMFRが、前記範囲の上限値以下であることにより、樹脂組成物の難燃性能を効果的に向上でき、前記範囲の下限値以上であることにより、樹脂組成物を含む成形体のウェルド強度を良好としうる。
本実施形態のポリプロピレン系樹脂組成物は、難燃性に優れ、かつ外観が良好な成形体(特に、射出成形体)を製造しうる。成形体の例としては、射出成形体、押出成形体、圧縮成形体、異型成形体、真空成形体、シート成形体、ロール成形体、熱プレス成形体、発泡成形体、インジェクションプレス成形体、ブロー成形体、及び、ガス注入成形体が挙げられる。成形体の寸法は、特に限定されないが、例えば、外寸が、縦0.5~2m、横0.5~2m、及び厚さ1~10mmである。成形体の形状は、例えば板状又は中空状としうる。本実施形態のポリプロピレン系樹脂組成物は、各種部材の材料(例えば、自動車の内外装部品及びエンジンルーム内部品、二輪車部品、電気製品の部品、各種コンテナー、家具)として好適に用いられうる。
自動車の内外装部品の例としては、インストロメントパネル、ドアートリム、ピラー、サイドプロテクター、コンソールボックス、コラムカバー、バンパー、フェンダー、ホイールカバーが挙げられる。自動車のエンジンルーム内部品の例としては、バッテリーケース、エンジンカバーが挙げられる。二輪車部品の例としては、カウリング、マフラーカバーが挙げられる。
本実施形態のポリプロピレン系樹脂組成物は、任意の方法で製造しうる。
例えば、ポリプロピレン系樹脂組成物は、シリンダ及び二本のスクリューを備える二軸混練押出機中で、ポリプロピレン系重合体(A)、難燃剤(B)、ガラス繊維(C)、及び必要に応じて添加される任意成分を、混練することにより製造しうる。
好ましくは、ポリプロピレン系重合体(A)と難燃剤(B)とを含む原料(1)を、前記二軸混練押出機のシリンダ内に、前記二本のスクリューの上流側における端からの距離L1の位置で供給し、前記ガラス繊維(C)を、前記シリンダ内に、前記二本のスクリューの上流側における端からの距離L2の位置で供給する。ここで、L1/Lは、好ましくは0以上0.3未満の範囲であり、L2/Lは、好ましくは0.3~0.9の範囲である。
本発明の一実施形態に係る成形体は、前記ポリプロピレン系樹脂組成物を含む。本実施形態に係る成形体は、ポリプロピレン系樹脂組成物からなり、ポリプロピレン系樹脂組成物を成形することにより形成されうる。本実施形態に係る成形体は、前記ポリプロピレン系樹脂組成物を含んでいるので、難燃性に優れ、かつ外観が良好である。
成形体としては、射出成形法により成形された、射出成形体が好ましい。
(メルトフローレート(MFR、単位:g/10分))
JIS K7210-1:2014及びK7210-2:2014に規定された方法に従い、荷重2.16kgf、温度230℃の条件で測定した。
樹脂組成物2gを、沸騰しているp-キシレン中で2時間溶解して、ガラス繊維を含む、キシレン不溶成分を得た。次いで、キシレン不溶成分中のガラス繊維を、マイクロスコープを用いて観察し、ガラス繊維200本の長さ及び径を測定した。重量平均繊維長及び平均繊維径を算出し、重量平均繊維長の平均繊維径に対する比を、樹脂組成物に含まれるガラス繊維のアスペクト比とした。
重量平均繊維長は、下記式に従い算出した。
重量平均繊維長(Lw)=(Σqi×Li2)/(Σqi×Li)
ここで、Liはガラス繊維の長さ(繊維長)であり、qiは、繊維長Liを有するガラス繊維の本数である。
樹脂組成物を、射出成形機(東芝機械株式会社製「IS100EN」)を用いて射出成形し、160mm(縦)×160mm(横)×2.0mm(厚さ)の試験平板を作成した。成形条件は、成形温度220℃、金型冷却温度50℃とした。得られた試験平板の外観を目視により観察し、下記の基準にしたがって評価した。
良好(○):試験平板の表面にガラス繊維の浮き出しが目立たない。
不良(×):試験平板の表面にガラス繊維の浮き出しが目立つ。
樹脂組成物を射出成形機:住友重機械工業社製「SYCAP110」に供給して、成形温度230℃、金型冷却温度50℃の条件により射出成形を行い、127mm(長さ)×13mm(幅)×1.6mm(厚さ)の試験片を作製した。得られた試験片を用いてUL94-V規格に従い試験片の難燃性を評価した。難燃性はV-0がV-1より優れ、V-1はV-2より優れている。
樹脂組成物を射出成形機:東芝機械株式会社製「IS100EN」に供給して、成形温度220℃、金型冷却温度50℃の条件により射出成形を行い、160mm(縦)×160mm(横)×2.0mm(厚さ)の試験平板を作製した。得られた試験平板を用いて規格UL94-5Vに基づいてプラーク(Plaque)試験を行った。前記得られた厚さ2.0mmの試験平板を127mm(長さ)×13mm(幅)×2.0mm(厚さ)に切り出して試験片を得、規格UL94-5Vに基づいてバー(Bar)試験を行った。
プラーク試験及びバー試験の基準を満たした場合、評価を5VAとした。
実施例及び比較例において使用した原料を下記に示す。
ポリプロピレン系重合体としての、プロピレン単独重合体(A-1)~(A-3)を、特開2004-182981号公報の実施例1記載の方法によって得られる重合触媒を用いて、プロピレンから気相重合法により製造した。製造条件は、重合体(A-1)~(A-3)が、それぞれ下記物性を有するような条件とした。
MFR:(230℃、荷重2.16kgf):14g/10分
プロピレン単独重合体(A-2)
MFR:(230℃、荷重2.16kgf):120g/10分
プロピレン単独重合体(A-3)
MFR:(230℃、荷重2.16kgf):240g/10分
リン含有難燃剤として、リン酸メラミン及びリン酸ピペリジンを主成分とする難燃剤(製品名:アデカスタブFP-2200S、ADEKA社製)を用いた。
ガラス繊維(C-1)~(C-3)として、下記のガラス繊維を用いた。
ガラス繊維(C-1):チョップドストランド1
直径:10μm
繊維長:4mm
直径:11μm
繊維長:78μm
直径:10μm
繊維長:9mm
プロピレン重合体のパウダー(極限粘度数[η]=3.0dL/g、エチレン単位含量0.2重量%)100重量部に、無水マレイン酸を1.0重量部、ジ-(tert-ブチルパーオキシ)ジイソプロピルベンゼン(製品名:パーブチルP、日本油脂社製)を0.14重量部、ジセチルパーオキシジカルボネート(製品名:パーカドックス24FL、化薬アクゾ社製)を0.05重量部、ステアリン酸カルシウム(製品名:AR-2、堺化学工業社製)を0.05重量部、酸化防止剤としてペンタエリスリトールテトラキス[3-(3,5-ジ-tert-ブチル-4-ヒドロキシフェニル)プロピオネート](製品名:Songnox1010、SONGWON社製)を0.3重量部を添加して十分に予備混合した。次いで、予備混合物を二軸押出機の供給口より供給して混練を行い、無水マレイン酸変性ポリプロピレン系重合体を得た。得られた酸変性ポリプロピレン系重合体としての無水マレイン酸変性ポリプロピレン系重合体は、MFR(230℃、荷重2.16kgf)が170g/10分、無水マレイン酸単位の含有量が0.32(重量%)であった。
(ポリプロピレン系樹脂組成物の製造)
表1-1に示す配合の、(A)成分(ポリプロピレン系重合体)、(D)成分(酸変性ポリプロピレン系重合体)、及び(B)成分(リン含有難燃剤)と、中和剤としてステアリン酸カルシウム(製品名:カルシウムステアレートS、日本油脂社製)0.05重量部、酸化防止剤として3,9-ビス[2-(3-(3-tert-ブチル-4-ヒドロキシ-5-メチルフェニル)プロピオニルオキシ)-1,1-ジメチルエチル]-2,4,8,10-テトラオキサスピロ[5.5]ウンデカン(製品名:SumilizerGA80、住友化学社製)0.1重量部、3,9-ビス(2,4-ジ-tert-ブチルフェノキシ)-2,4,8,10-テトラオキサスピロ[5.5]ウンデカン(製品名:Songnox6260、SONGWON社製)0.2重量部、及びジミリスチル-3,3-チオジプロピオネート(製品名:SumilizerTPM、住友化学社製)0.2重量部、有機過酸化物マスターバッチとして1,3-ジ-(2-tert-ブチルパーオキシイソプロピル)ベンゼンを含む樹脂ペレット(製品名:CH-11、化薬ヌーリオン社製、有機過酸化物成分8%含有)0.6重量部とを、二軸混練押出機のメインホッパーから供給して、温度200~230℃、スクリュー回転数400rpmで溶融混練した。スクリューの全長をLとし、スクリューの上流側の端部からのメインホッパーまでの距離をL1とすると、L1/L=0.05であった。中和剤、酸化防止剤、有機過酸化物マスターバッチの使用量は、(A)成分、(D)成分、(B)成分、及び(C)成分の合計重量を100質量部とした場合の値である。
ペレットを熱風乾燥器中100℃で2時間乾燥し、評価に供するポリプロピレン系樹脂組成物のペレットを得た。得られたポリプロピレン系樹脂組成物のペレットを、前記の方法で成形して試験片又は試験平板を得て、評価した。評価結果を表2-1に示す。
表1-1に示す配合の、(A)成分(ポリプロピレン系重合体)、(D)成分(酸変性ポリプロピレン系重合体)、(B)成分(リン含有難燃剤)、(C)成分(ガラス繊維)を用いた。また、前記(A)成分、(D)成分、(B)成分、及び、(C)成分の合計重量を100重量部として、0.58重量部の有機過酸化物マスターバッチ(製品名:CH-11、化薬ヌーリオン社製、有機過酸化物成分8%含有)を用いた。
以上の事項以外は、実施例1と同様の手順を行って、評価に供するポリプロピレン系樹脂組成物のペレットを得た。得られたポリプロピレン系樹脂組成物のペレットを、前記の方法で成形して試験片又は試験平板を得て、評価した。評価結果を表2-1に示す。
表1-1~表1-2に示す配合の、(A)成分(ポリプロピレン系重合体)、(D)成分(酸変性ポリプロピレン系重合体)、(B)成分(リン含有難燃剤)、(C)成分(ガラス繊維)を用いた。また、有機過酸化物マスターバッチ(製品名:CH-11、化薬ヌーリオン社製、有機過酸化物成分8%含有)を用いなかった。
以上の事項以外は、実施例1と同様の手順を行って、評価に供するポリプロピレン系樹脂組成物のペレットを得た。得られたポリプロピレン系樹脂組成物のペレットを、前記の方法で成形して試験片又は試験平板を得て、評価した。評価結果を表2-1~表2-2に示す。
表1-2に示す配合の、(A)成分(ポリプロピレン系重合体)、(D)成分(酸変性ポリプロピレン系重合体)、(B)成分(リン含有難燃剤)、(C)成分(ガラス繊維)を用いた。また、前記(A)成分、(D)成分、(B)成分、及び、(C)成分の合計重量を100重量部として、0.30重量部の有機過酸化物マスターバッチ(製品名:CH-11、化薬ヌーリオン社製、有機過酸化物成分8%含有)を用いた。
以上の事項以外は、実施例1と同様の手順を行って、評価に供するポリプロピレン系樹脂組成物のペレットを得た。得られたポリプロピレン系樹脂組成物のペレットを、前記の方法で成形して試験片又は試験平板を得て、評価した。評価結果を表2-2に示す。
(ポリプロピレン系樹脂組成物の製造)
表1-3に示す配合の、(A)成分(ポリプロピレン系重合体)、(D)成分(酸変性ポリプロピレン系重合体)、(B)成分(リン含有難燃剤)、(C)成分(ガラス繊維)と、前記(A)成分、(D)成分、(B)成分、及び、(C)成分の合計重量を100重量部として、中和剤としてステアリン酸カルシウム(製品名:カルシウムステアレートS、日本油脂社製)0.05重量部、酸化防止剤として3,9-ビス[2-(3-(3-tert-ブチル-4-ヒドロキシ-5-メチルフェニル)プロピオニルオキシ)-1,1-ジメチルエチル]-2,4,8,10-テトラオキサスピロ[5.5]ウンデカン(製品名:SumilizerGA80、住友化学社製)0.1重量部、3,9-ビス(2,4-ジ-tert-ブチルフェノキシ)-2,4,8,10-テトラオキサスピロ[5.5]ウンデカン(製品名:Songnox6260、SONGWON社製)0.2重量部、及びジミリスチル-3,3-チオジプロピオネート(製品名:SumilizerTPM、住友化学社製)0.2重量部とを、二軸混練押出機のメインホッパーから供給して、温度200~230℃、スクリュー回転数400rpmで溶融混練した。スクリューの全長をLとし、スクリューの上流側の端部からのメインホッパーまでの距離をL1とすると、L1/L=0.05であった。
ペレットを熱風乾燥器中100℃で2時間乾燥し、評価に供するポリプロピレン系樹脂組成物のペレットを得た。得られたポリプロピレン系樹脂組成物のペレットを、前記の方法で成形して試験片又は試験平板を得て、評価した。評価結果を表2-3に示す。
表1-3に示す配合の、(A)成分(ポリプロピレン系重合体)、(D)成分(酸変性ポリプロピレン系重合体)、(B)成分(リン含有難燃剤)、(C)成分(ガラス繊維)を用いた。また、(A)成分、(D)成分、(B)成分、及び(C)成分の合計重量を100重量部として、0.30重量部の有機過酸化物マスターバッチ(製品名:CH-11、化薬ヌーリオン社製、有機過酸化物成分8%含有)を用いた。
以上の事項以外は、実施例1と同様の手順を行って、評価に供するポリプロピレン系樹脂組成物のペレットを得た。得られたポリプロピレン系樹脂組成物のペレットを、前記の方法で成形して試験片又は試験平板を得て、評価した。評価結果を表2-3に示す。
実施例及び比較例において用いた各成分の配合、及びガラス繊維の供給方法を、表1-1~表1-3に示した。
下表において、略称は以下の意味を表す。
「PP」:ポリプロピレン系重合体
「A-1(MFR:14)」:プロピレン単独重合体(A-1)
「A-2(MFR:120)」:プロピレン単独重合体(A-2)
「A-3(MFR:240)」:プロピレン単独重合体(A-3)
「酸変性PP」:酸変性ポリプロピレン系重合体
「MPA]:無水マレイン酸変性ポリプロピレン系重合体
「FP2200S」:難燃剤(製品名:アデカスタブFP-2200S、ADEKA社製)
「GF」:ガラス繊維
「C-1」:ガラス繊維(C-1)(チョップドストランド1)
「C-2」:ガラス繊維(C-2)(ミルドファイバー)
「C-3」:ガラス繊維(C-3)(チョップドストランド2)
「CH-11」:有機過酸化物マスターバッチ(製品名:CH-11、化薬ヌーリオン社
製、有機過酸化物成分8%含有)
「二軸-side」:ガラス繊維を、二軸混練押出機のサイドフィーダーから供給したことを示す。
「二軸-main」:ガラス繊維を、二軸混練押出機のメインホッパーから供給したことを示す。
樹脂組成物の組成及び評価結果を、下表に示す。
表中の燃焼試験(UL94 5V)の項目で評価が記載されていない欄は、燃焼試験(UL94 5V)の評価が行われていないことを示す。
表中の略語は下記の意味を示す。
「1.6mmt」:厚み1.6mm
「2.0mmt」:厚み2.0mm
実施例1~9に係る、アスペクト比が20~60であるガラス繊維を含むポリプロピレン系樹脂組成物から形成された成形品は、UL94-V規格による難燃性の評価が優れている。一方、比較例1~2に係る、アスペクト比が20未満であるガラス繊維を含むポリプロピレン系樹脂組成物から形成された成形品は、UL94-V規格による燃焼性の評価が劣る。比較例3に係る、アスペクト比が60より大きいガラス繊維を含むポリプロピレン系樹脂組成物から形成された成形品は、外観が不良である。
101 シリンダ
110 スクリュー
111 スクリューの端部
112 スクリューの端部
130 メインホッパー
140 サイドフィーダー
Claims (6)
- ポリプロピレン系重合体(A)と、難燃剤(B)と、アスペクト比が20~60であるガラス繊維(C)とを含むポリプロピレン系樹脂組成物。
- ガラス繊維(C)の長さが、200~600μmである、請求項1に記載のポリプロピレン系樹脂組成物。
- さらに酸変性ポリオレフィン系重合体(D)を含む、請求項1又は2に記載のポリプロピレン系樹脂組成物。
- ポリプロピレン系樹脂組成物の全量を100重量%としたときに、
ポリプロピレン系重合体(A)の含有量が30~70重量%であり、
難燃剤(B)の含有量が5~50重量%であり、
ガラス繊維(C)の含有量が5~40重量%である、
請求項1~3のいずれか一項に記載のポリプロピレン系樹脂組成物。 - 請求項1~4のいずれか一項に記載のポリプロピレン系樹脂組成物を含む、成形体。
- 外寸が、縦0.5~2m、横0.5~2m、及び厚さ1~10mmである、請求項5に記載の成形体。
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WO2024029197A1 (ja) * | 2022-08-05 | 2024-02-08 | 住友化学株式会社 | ポリプロピレン系樹脂組成物及びこれを含む成形体 |
WO2024084885A1 (ja) * | 2022-10-19 | 2024-04-25 | 三菱ケミカル株式会社 | 樹脂組成物、樹脂製品の製造方法及び難燃剤マスターバッチ |
WO2024172164A1 (ja) * | 2023-02-17 | 2024-08-22 | 株式会社プライムポリマー | 強化ポリプロピレン樹脂組成物 |
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