Classifications

• • 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
  • C08K3/02—Elements
  • C08K3/04—Carbon
• • 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
  • C08K3/32—Phosphorus-containing compounds
• • 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
  • C08K5/49—Phosphorus-containing compounds
• • 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 reinforced polypropylene resin composition that can produce molded articles with excellent mechanical properties and flame retardancy.
• Polypropylene resin molded bodies reinforced with glass fibers are lightweight and have excellent rigidity and heat resistance, making them useful in a wide range of fields, including electrical equipment, automobiles, housing facilities, and medical equipment.
• molded articles made of glass fiber-reinforced polypropylene resin containing flame retardants are expected to be used in a wide range of applications requiring flame retardancy.
• such molded articles may not have high commercial value in terms of appearance because the glass fibers, flame retardants, and other inclusions appear on the surface of the molded article, and improvements in this area are required.
• Patent Document 1 discloses a reinforced polypropylene resin composition in which polypropylene resin is blended with glass fiber, a flame retardant, and acid-modified polypropylene, and aims to provide a molded product that satisfies UL94 V-0 and has minimal warping while maintaining a high level of mechanical properties.
• Patent Document 2 discloses a reinforced polypropylene resin composition in which a polypropylene resin is blended with glass fiber, two types of flame retardants, and maleic anhydride-modified polypropylene, and aims to provide a resin composition having excellent flame retardancy, mechanical properties, and flowability.
• a polypropylene resin is blended with glass fiber, two types of flame retardants, and maleic anhydride-modified polypropylene, and aims to provide a resin composition having excellent flame retardancy, mechanical properties, and flowability.
• none of the patent documents points out the commercial value of the molded article in terms of its surface and appearance.
• the present invention provides a molded article made of a reinforced polypropylene resin composition in which polypropylene resin is blended with glass fiber, a flame retardant, and an acid-modified polypropylene resin, and while maintaining the same level of flame retardancy and mechanical properties, the molded article has high commercial value in terms of its appearance.
• a reinforced polypropylene resin composition comprising:
• the reinforced polypropylene resin composition further contains carbon black in an amount of 0.1 to 2 parts by mass per 100 parts by mass of the total of the polypropylene resin (A), the phosphorus-based flame retardant (B), and the glass fiber (C). Reinforced polypropylene resin composition according to any one of (I) to (V).
• the present invention makes it possible to provide a molded article made of a reinforced polypropylene resin composition in which polypropylene resin is blended with glass fiber, a flame retardant, and an acid-modified polypropylene resin, while maintaining the same level of flame retardancy and mechanical properties, and providing a molded article with high commercial value in terms of its appearance.
• the polypropylene resin (A), the phosphorus-based flame retardant (B) and the glass fiber (C) that constitute the reinforced polypropylene resin composition of the present invention will be described below.
• the polypropylene resin (A) comprises an unmodified polypropylene resin (A-1) and an acid-modified polypropylene resin (A-2).
• the unmodified polypropylene resin (A-1) (sometimes referred to as unmodified PP (A-1)) includes polypropylene homopolymers and copolymers of propylene with ⁇ -olefins such as ethylene and butene.
• the copolymers include random copolymers or block copolymers of propylene with at least one ⁇ -olefin selected from ethylene and ⁇ -olefins having 4 to 20 carbon atoms.
• the content of the propylene skeleton in the random copolymer is usually 90 to 99 mol%, preferably 92 to 98 mol%.
• the content of the propylene skeleton in the block copolymer is usually 70 to 99 mol%, preferably 75 to 98 mol%.
• the unmodified polypropylene resin (A-1) two or more polypropylene-based resins (for example, polypropylene homopolymers and propylene-based copolymers) may be used in combination.
• the unmodified polypropylene resin (A-1) contains a propylene-based copolymer
• specific examples of monomers other than propylene used in the propylene-based copolymer include ethylene, 1-butene, 2-methyl-1-propene, 2-methyl-1-butene, 3-methyl-1-butene, 1-pentene, 1-hexene, 2-ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-
• the alkyl ether include 1-butene, 1-heptene, methyl-1-hexene, dimethyl-1-pentene, ethyl-1-pentene, trimethyl-1-butene, methylethyl-1-butene, 1-octene, methyl-1-pentene, ethyl-1-hexene, dimethyl-1-hexene, propyl-1
• the biomass-derived or chemically recycled propylene monomer unmodified polypropylene resin (A-1) may contain biomass-derived propylene as a monomer constituting the polymer.
• the propylene constituting the polymer may be only biomass-derived propylene, or may contain both biomass-derived propylene and fossil fuel-derived propylene.
• Biomass-derived propylene is propylene obtained from any renewable natural raw material, such as fungi, yeast, algae, and bacteria, or from an animal or plant source, and its residues. It contains 14C isotopes as carbon at a ratio of about 10-12 , and has a biomass carbon concentration (pMC) of about 100 (pMC) measured in accordance with ASTM D 6866.
• the unmodified polypropylene resin (A-1) may contain chemically recycled propylene as a monomer constituting the polymer.
• the propylene constituting the polymer may be only chemically recycled propylene, or may contain chemically recycled propylene and fossil fuel-derived propylene and/or biomass-derived propylene. Chemically recycled propylene is obtained by a conventionally known method.
• the melt flow rate (MFR) of the unmodified polypropylene resin (A-1) measured in accordance with ASTM D1238 at 230° C. under a load of 2.16 kg is 100 to 400 g/10 min, preferably 150 to 350 g/10 min, more preferably 200 to 300 g/10 min. If the melt flow rate (MFR) is less than 100, the dispersion of the glass fiber and the flame retardant is poor, and the strength and appearance of the molded article obtained from the reinforced polypropylene resin composition are reduced, and the product with high commercial value tends not to be obtained. If the melt flow rate (MFR) is more than 400, the toughness of the reinforced polypropylene resin composition is reduced, and pelletization during production may not be possible.
• the MFR of the unmodified PP (A-1) is within the range of the present invention, the composition is excellent in strength such as impact strength and appearance as well as in flame retardancy. The reason for this is unclear, but the present inventors speculate that this is because the impregnation of the glass fiber and the flame retardant is improved and the dispersion in the unmodified PP is improved. The present inventors have found that, if the MFR of the unmodified PP is within the range of the present invention, the Charpy impact tends to be maintained (or is unlikely to decrease) even if the flame retardant (B) is added to the system of unmodified PP (A-1)/modified PP (A-2)/glass fiber (C). Furthermore, when the MFR of the unmodified polypropylene resin (A-1) is within this range, it can be molded at low temperatures, which is advantageous in that the flame retardancy is easily maintained during recycling or reuse.
• the unmodified polypropylene resin (A-1) is preferably an isotactic polypropylene resin.
• An isotactic polypropylene resin is a polypropylene resin having an isotactic pentad fraction determined by NMR of 0.9 or more, preferably 0.95 or more.
• the unmodified polypropylene resin (A-1) is generally prepared using a Ziegler-Natta catalyst, a metallocene catalyst, or the like.
• the acid-modified polypropylene resin (A-2) (sometimes referred to as modified PP (A-2)) used in the present invention is a resin obtained by reacting a polypropylene resin with an acid-modified monomer, and is a resin having monomer units derived from the acid-modified monomer in the molecule.
• the polypropylene resin used for acid modification is, for example, the polymer exemplified as the unmodified polypropylene resin (A-1) described above.
• the melt flow rate (MFR) of the polypropylene resin used can be appropriately determined, taking into account that the average molecular weight of the polymer in the resin changes (generally decreases) due to the acid modification reaction.
• Acid-modified monomers used for acid modification include unsaturated carboxylic acids such as maleic acid, fumaric acid, itaconic acid, acrylic acid, methacrylic acid, citraconic acid, crotonic acid, isocrotonic acid, endo-cis-bicyclo[2.2.1]hept-2,3-dicarboxylic acid (Nadic acid, trademark), and methyl-endo-cis-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid (methyl Nadic acid, trademark).
• unsaturated carboxylic acids such as maleic acid, fumaric acid, itaconic acid, acrylic acid, methacrylic acid, citraconic acid, crotonic acid, isocrotonic acid, endo-cis-bicyclo[2.2.1]hept-2,3-dicarboxylic acid (Nadic acid, trademark), and methyl-endo-cis-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic
• examples of 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.
• maleic acid and acrylic acid as the unsaturated carboxylic acid
• the acid modification may be carried out by a conventional method, for example, a method of grafting an acid-modified monomer onto a polypropylene resin.
• the acid-modified monomer may be grafted onto a polypropylene resin that serves as a graft main chain in the presence of a radical polymerization initiator.
• a conventionally known method can be used, for example, a melt kneading method or a solution method.
• polypropylene resin and an acid-modified monomer are kneaded together with a radical polymerization initiator in an extruder, and the acid-modified monomer is graft-copolymerized to modify the resin.
• radical polymerization initiators include organic peroxides and azo compounds.
• organic peroxides include benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, m-trioyl peroxide, di-t-butyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexane, 2,5-dimethyl-2,5-bis(t-butylperoxy)hexyne-3, lauroyl peroxide, t-butyl peroxy acetate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butyl peroxybenzoate, t-butyl peroxy isobutyrate, t-butyl peroxy phenyl acetate, t-butyl peroxy s-octate, t-butyl peroxy pivalate, cumyl peroxy pivalate,
• azo compounds examples include azoisobutyronitrile and dimethylazoisobutyrate.
• radical polymerization initiators can be used.
• the polypropylene resin is suspended or dissolved in a solvent, and then the acid-modifying monomer and radical polymerization initiator are added and mixed at a temperature of usually 80 to 200°C to cause graft polymerization.
• Solvents used in the solution method include, for example, aromatic hydrocarbon solvents such as toluene and xylene, aliphatic hydrocarbon solvents such as hexane, heptane, octane and decane, alicyclic hydrocarbon solvents such as cyclohexane and methylcyclohexane, chlorinated hydrocarbon solvents such as trichloroethylene, perchloroethylene, dichloroethylene, dichloroethane and chlorobenzene, aliphatic alcohol solvents such as ethanol and isopropanol, ketone solvents such as acetone, methyl isobutyl ketone and methyl ethyl ketone, and ester solvents such as methyl acetate, ethyl acetate and butyl acetate.
• aromatic hydrocarbon solvents such as toluene and xylene
• aliphatic hydrocarbon solvents such as hexane, heptane
• radical polymerization initiators that can be used include the peroxides mentioned above.
• the melt flow rate (MFR) (190° C., 2.16 kg load) of the acid-modified polypropylene resin (A-2) is 100 to 1000 g/10 min, preferably 100 to 750 g/10 min, and more preferably 100 to 500 g/10 min.
• MFR melt flow rate
• the graft amount of the acid-modified monomer in the acid-modified polypropylene resin (A-2) is 0.5 to 3.0% by mass. Of these, 0.3 to 2.0% by mass is preferable, and 0.5 to 1.5% by mass is particularly preferable.
• the graft amount (mass %) of the acid-modified monomer is the proportion of the monomer derived from the acid-modified monomer in the acid-modified polypropylene resin (A-2), i.e., the proportion of the monomer that is not removed by the solvent (reflecting the monomer that is chemically bonded to the main chain of the polypropylene resin), expressed as the proportion (mass %) in the acid-modified polypropylene resin (A-2).
• the acid-modified polypropylene resin (A-2) is completely dissolved in boiling p-xylene by heating, and the p-xylene solution containing the acid-modified propylene resin (A-2) is allowed to cool, and then acetone is added and stirred to precipitate a polymer.
• the precipitated polymer is filtered and dried to obtain a purified polymer.
• the proportion (mass%) of monomers derived from the acid-modified monomer contained in the purified polymer is defined as the graft amount (mass%) of the acid-modified monomer.
• the graft amount (mass %) can be measured and calculated using infrared absorption spectroscopy, NMR spectroscopy, or the like.
• the graft efficiency (%) of the acid-modified monomer of the acid-modified polypropylene resin (A-2) is more than 60%. That is, the graft efficiency (%) of the acid-modified polypropylene resin (A-2) is measured when it is used to prepare a reinforced polypropylene resin composition, or when it is used as a component when molding a molded article from the reinforced polypropylene resin composition.
• This graft efficiency (%) is preferably more than 60%, and more preferably more than 65%.
• the graft efficiency (%) of the acid-modified monomer in the acid-modified polypropylene resin (A-2) is less than 60%, the strength of the molded article obtained from the reinforced polypropylene resin composition decreases, and the appearance is not satisfactory, so that it is difficult to obtain a product with high commercial value.
• the grafting efficiency (%) of the acid-modified monomer can be determined as follows. That is, the mass X (g/100 g of sample polymer) of the monomer derived from the acid-modified monomer contained in the sample of acid-modified polypropylene resin (A-2) (including the monomer chemically bonded to the main chain of the polymer of the polypropylene resin, and the monomer not chemically bonded to the main chain of the polymer in the graft reaction, which is dissolved by the solvent and remains in the resin) is calculated.
• the mass Y (g/100 g of sample polymer) of the monomer derived from the acid-modified monomer that is not removed by the solvent (reflecting the monomer chemically bonded to the main chain of the polymer) is determined.
• the mass X (g) of the acid-modified monomer contained in the acid-modified polypropylene resin (A-2) (including a monomer derived from the acid-modified monomer chemically bonded to the main chain of the polymer, and a monomer remaining in the resin that is not chemically bonded to the main chain of the polymer and is dissolved by the solvent in the graft reaction) can be determined by pressing the acid-modified polypropylene resin (A-2) into a film and subjecting the film to Fourier transform infrared spectroscopy (FT-IR) from the intensity ratio of the infrared absorption peaks at 1780 cm -1 and 974 cm -1 .
• FT-IR Fourier transform infrared spectroscopy
• the mass Y (g) of the acid-modified monomer that is not removed by the solvent (reflecting the monomer derived from the acid-modified monomer that is chemically bonded to the main chain of the polymer) after the operation of removing the acid-modified monomer from the acid-modified polypropylene resin (A-2) with a solvent is obtained by taking about 2 g of the acid-modified polypropylene resin, completely heating and dissolving it in 500 ml of boiling p-xylene, cooling it, and then pouring it into 1200 m of acetone, filtering the precipitate, and removing the maleic anhydride that has not contributed to the graft reaction in the resin.
• a film is made from the polymer precipitate by pressing, and the intensity ratio of the infrared absorption peaks at 1780 cm -1 and 974 cm -1 is similarly obtained by Fourier transform infrared spectroscopy (FT-IR).
• FT-IR Fourier transform infrared spectroscopy
• the melting point of the acid-modified polypropylene resin (A-2) is 150 to 170°C.
• the phosphorus-based flame retardant (B) includes red phosphorus compounds, phosphate compounds, phosphoric acid esters, phosphinates, phosphazene compounds, etc., among which the phosphate compounds are preferred.
• the phosphate compounds include not only phosphates but also polyphosphoric acids such as diphosphoric acid (pyrophosphoric acid) and triphosphoric acid, as well as salts of phosphorous acid and hypophosphorous acid (phosphinic acid).
• Examples of the phosphate salt include salts with the above-mentioned various phosphoric acids, and salts with ammonium and nitrogen compounds such as piperazine and melamine.
• ammonium salts include ammonium phosphate, ammonium dihydrogen phosphate, and diammonium hydrogen phosphate.
• polyphosphates examples include ammonium polyphosphate and ammonium amide polyphosphate.
• phosphates examples include the following:
• aliphatic diamines examples include N,N,N',N'-tetramethyldiaminomethane, ethylenediamine, N,N'-dimethylethylenediamine, N,N'-diethylethylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetraethylethylenediamine, 1,2-propanediamine, 1,3-propanediamine, tetramethylenediamine, and pentamethylenediamine.
• the amine compounds containing a piperazine ring include piperazine, ans-2,5-dimethylpiperazine, and 4-bis(2-aminoethyl)piperazine.
• Examples of the amine compounds containing a triazine ring include melamine, acetoguanamine, benzoguanamine, acrylguanamine, 2,4-diamino-6-nonyl-1,3,5-triazine, and 2,4-diamino-6-hydroxy-1,3,5-triazine.
• salts of nitrogen compounds such as piperazine and melamine are preferred, and among these, at least one compound selected from the group consisting of piperazine phosphate, piperazine pyrophosphate, and piperazine polyphosphate is preferred.
• phosphazene compound examples include phenoxyphosphazene, (poly)tolyloxyphosphazene (e.g., o-tolyloxyphosphazene, o,p-tolyloxyphosphazene, etc.), (poly)xylyloxyphosphazene, (poly)phenoxytolyloxyphosphazene (e.g., phenoxy o-tolyloxyphosphazene, phenoxy m-tolyloxyphosphazene, etc.), (poly)phenoxyxylyloxyphosphazene, (poly)phenoxytolyloxyxylyloxyphosphazene, etc.
• the content of the phosphorus-based flame retardant (B) in the reinforced polypropylene resin composition is 15 to 40 mass %.
• the total of the polypropylene resin (A), the phosphorus-based flame retardant (B), and the glass fiber (C) is 100% by mass.
• the content of the phosphorus-based flame retardant (B) is preferably in the range of 20 to 35 mass %. If the amount of the phosphorus-based flame retardant (B) is small, the molded article of the reinforced polypropylene resin will not have adequate flame retardancy, and if the amount of the phosphorus-based flame retardant (B) is too large, the molded article will tend not to have sufficient commercial value in terms of appearance. Furthermore, phosphorus-based flame retardants are non-halogen flame retardants and therefore are environmentally friendly.
• the type of glass fiber (C) is not particularly limited, and may be any of E glass, S glass, C glass, and A glass.
• the fiber diameter is also not particularly limited, but is usually 5 to 25 ⁇ m, preferably 6 to 20 ⁇ m.
• the preferred form of glass fiber (C) is chopped strands.
• Chopped strands usually have a length of 1.5 to 10 mm and a fiber diameter of 5 to 25 ⁇ m, preferably a length of 3 to 6 mm and a fiber diameter of 6 to 17 ⁇ m.
• continuous fiber bundles can also be used. Continuous fiber bundles are commercially available, for example, as rovings.
• the fiber diameter is usually 5 to 25 ⁇ m, preferably 10 to 20 ⁇ m.
• the glass fiber (C) can be used as is, but it is preferable that it has been surface-treated with a treatment agent such as an organic titanate coupling agent, an organic silane coupling agent, a modified polyolefin grafted with an unsaturated carboxylic acid or its anhydride, a fatty acid, a fatty acid metal salt, or a fatty acid ester.
• a treatment agent such as an organic titanate coupling agent, an organic silane coupling agent, a modified polyolefin grafted with an unsaturated carboxylic acid or its anhydride, a fatty acid, a fatty acid metal salt, or a fatty acid ester.
• a treatment agent such as an organic titanate coupling agent, an organic silane coupling agent, a modified polyolefin grafted with an unsaturated carboxylic acid or its anhydride, a fatty acid, a fatty acid metal salt, or a fatty acid ester.
• the reinforced polypropylene resin composition of the present invention may contain additives such as other resins, heat stabilizers, antistatic agents, weather stabilizers, light stabilizers, antioxidants, antioxidants, copper inhibitors, fatty acid metal salts, softeners, dispersants, fillers, colorants, pigments, and foaming agents, as necessary, within the scope of the present invention.
• additives such as other resins, heat stabilizers, antistatic agents, weather stabilizers, light stabilizers, antioxidants, antioxidants, copper inhibitors, fatty acid metal salts, softeners, dispersants, fillers, colorants, pigments, and foaming agents, as necessary, within the scope of the present invention.
• the order of mixing the additives is arbitrary, and they may be mixed simultaneously, or a multi-stage mixing method in which some components are mixed and then other components are mixed may be used. Among these, it is preferable to mix carbon black, phenol-based antioxidants, and/or sulfur-based antioxidants.
• the carbon black is contained in an amount of 0.1 to 2 parts by mass per 100 parts by mass of the total of the polypropylene resin (A), the phosphorus-based flame retardant (B), and the glass fiber (C) in the reinforced polypropylene resin composition of the present invention.
• the reinforced polypropylene resin composition of the present invention comprises: Polypropylene resin (A) 10 to 70% by mass, Phosphorus-based flame retardant (B) 15 to 40 mass%, and glass fiber (C) 15 to 60% by mass Among them, the composition contains 20 to 60 mass% of polypropylene resin (A), Phosphorus-based flame retardant (B) 20 to 35 mass %, and glass fiber (C) 20 to 50% by mass It is preferable that Polypropylene resin (A) 23 to 49% by mass, Phosphorus-based flame retardant (B) 20 to 32 mass%, Glass fiber (C) is 25 to 45% by mass. In this range, the addition of polypropylene resin component (A) is particularly effective. (The total of the polypropylene resin (A), the phosphorus-based flame retardant (B), and the glass fiber (C) is 100% by mass.)
• the reinforced polypropylene resin composition preferably contains the acid-modified polypropylene resin (A-2) in a proportion of 0.1 to 3 mass%, more preferably 0.5 to 2 mass%.
• the total of the unmodified polypropylene resin (A-1), the acid-modified polypropylene resin (A-2), the phosphorus-based flame retardant (B), and the glass fiber (C) is 100% by mass.
• the reinforced polypropylene resin composition of the present invention has high impact resistance.
• This composition can be made into pellets, and may be short glass fiber pellets containing short fibers as the glass fibers (C) or long glass fiber pellets containing long fibers as the glass fibers (C).
• the reinforced polypropylene resin composition of the present invention can be produced by melt-kneading polypropylene resin (A), phosphorus-based flame retardant (B), glass fiber (C), and other components as necessary.
• the melt-kneading temperature is, for example, 5 to 100°C higher than the temperature at which the polymer of the contained components melts, and is preferably 10 to 60°C higher than the melting point of the polymer of the contained components that has the highest melting point.
• the melt-kneading processing time is, for example, 30 seconds or more and 15 minutes or less, and preferably 1 to 10 minutes.
• the glass fiber (C) of the reinforced polypropylene resin composition of the present invention is a short fiber, it can be produced by thoroughly melt-mixing and dispersing each component in an extruder using a roll mill, Banbury mixer, kneader, etc. It may also be dry-blended using a tumbler blender, Henschel mixer, ribbon mixer, etc., and melt-kneaded using a single-screw extruder, twin-screw extruder, etc. to produce a pellet-shaped molding material. In this method, the glass fiber (C) may be fed from either the top or side of the extruder. Also, in this method, all or a part of the components other than the glass fiber (C) may be melt-kneaded separately, and then melt-kneaded with the glass fiber (C).
• the reinforced polypropylene resin composition of the present invention can be processed into molded articles by ordinary molding methods such as injection molding, extrusion molding, and press molding.
• injection molding for example, the above-mentioned short glass fiber pellets or long glass fiber pellets can be used.
• other resins can be added when the short glass fiber pellets or long glass fiber pellets are fed from the hopper of the injection molding machine. It is also possible to side-feed the short glass fiber pellets or long glass fiber pellets from the bend port of the injection molding machine, feed other resins from the hopper, mix them in the injection molding machine, and mold them.
• polypropylene resin (A) can be melt-kneaded and molded in an injection molding machine without going through short glass fiber pellets or long glass fiber pellets.
• glass fiber (C) can be fed from the hopper of the injection molding machine, or side-fed from a vent port, etc.
• the molded article may be entirely formed from the reinforced polypropylene resin composition of the present invention, or may include a portion formed from the reinforced polypropylene resin composition of the present invention.
• Molded articles are used in a wide range of applications, from household items such as daily necessities and recreational uses to general industrial applications and industrial products. Examples include home appliance material parts, communication device parts, electrical parts, electronic parts, automobile parts, parts for vehicles other than automobiles, ships, aircraft materials, machine mechanism parts, building materials, civil engineering parts, agricultural materials, power tool parts, food containers, films, sheets, and fibers.
• Examples of home appliance material parts, communication equipment parts, electrical parts, and electronic parts include battery pack parts (covers, trays, module cases), printers, personal computers, word processors, keyboards, personal digital assistants (PDAs), headphone stereos, mobile phones, telephones, facsimiles, copiers, cards, holders, stationery, and other office and office equipment; home appliances such as washing machines, refrigerators, vacuum cleaners, microwave ovens, lighting fixtures, and game consoles.
• battery pack parts covers, trays, module cases
• printers personal computers, word processors, keyboards, personal digital assistants (PDAs), headphone stereos, mobile phones, telephones, facsimiles, copiers, cards, holders, stationery, and other office and office equipment
• home appliances such as washing machines, refrigerators, vacuum cleaners, microwave ovens, lighting fixtures, and game consoles.
• melt flow rate (MFR) (g/10 min)
• MFR melt flow rate
• A-1 unmodified polypropylene resin
• A-2 acid-modified polypropylene resin
• MFR acid-modified polypropylene resin
• the mass X (g/100 g sample polymer) of the acid-modified monomer contained in the acid-modified polypropylene resin (A-2) is determined from the intensity ratio of the infrared absorption peaks at 1780 cm ⁇ 1 and 974 cm ⁇ 1 by Fourier transform infrared spectroscopy (FT-IR) of a film prepared by pressing a sample polymer of the acid-modified polypropylene resin (A- 2 ) used in the reinforced polypropylene resin of the present invention.
• FT-IR Fourier transform infrared spectroscopy
• the mass Y (g/100g sample polymer) of the acid-modified monomer of the sample polymer after removing the acid-modified monomer from the acid-modified polypropylene resin (A-2) by a solvent when used for the reinforced polypropylene resin of the present invention is obtained by taking about 2 g of the acid-modified polypropylene resin, completely dissolving it in 500 ml of boiling p-xylene by heating, cooling, and then pouring it into 1200 m of acetone, filtering the precipitate, and removing the maleic anhydride that has not contributed to the graft reaction in the resin.
• a film is made from the polymer precipitate by pressing, and the mass Y is similarly obtained by Fourier transform infrared spectroscopy (FT-IR) from the intensity ratio of the infrared absorption peaks at 1780 cm -1 and 974 cm -1 .
• FT-IR Fourier transform infrared spectroscopy
• A-1-4 Made by Prime Polymer, a polypropylene homopolymer. MFR measured at 230°C under a load of 2.16 kg is 60 g/10 min.
• A-1-5) Made by Prime Polymer, a propylene-ethylene block copolymer. MFR measured at 230°C under a load of 2.16 kg is 90 g/10 min.
• a maleic anhydride-modified polypropylene having a melting point of 158°C as detected by a differential scanning calorimeter and a graft amount of maleic anhydride of 0.5% by mass (product name: Polybond 3200) (A-2-3) Made by Prime Polymer, Maleic anhydride-modified polypropylene (product name: ZP648) having an MFR of 30 g/10 min measured at 190° C. under a load of 2.16 kg, a melting point of 156° C. detected by a differential scanning calorimeter, and a graft amount of maleic anhydride of 0.3% by mass. (A-2-4) manufactured by Dow Chemical, MFR measured at 190° C. under a load of 2.16 kg is 400 g/10 min.
• a maleic anhydride-modified polypropylene having a melting point of 134°C as detected by a differential scanning calorimeter and a graft amount of maleic anhydride of 0.9% by mass (product name: Fusabond
• FP-2300S Phosphate-based flame retardant with piperazine phosphate as the main component (manufactured by ADEKA, product name: FP-2300S)
• T-480 Glass fiber (manufactured by Nippon Electric Glass, product name: T-480)
• Examples 1 to 8 and Comparative Examples 1 to 5 The unmodified polypropylene resin (A-1), acid-modified polypropylene resin (A-2), phosphorus-based flame retardant (B), carbon black master batch and other components shown in Table 1 were uniformly mixed in a tumbler mixer, and the mixture was fed to a co-rotating twin-screw kneader (TEX (registered trademark) 30 ⁇ , manufactured by The Japan Steel Works, Ltd.). Next, glass fiber (C) was side-fed from the middle of the twin-screw kneader and heated and kneaded at 210°C to obtain pellets of a fiber-reinforced reinforced polypropylene resin composition.
• TEX co-rotating twin-screw kneader
• an ISO No. 1 dumbbell test piece was molded in an injection molding machine (FANUC) at a molding temperature of 220° C. and a mold temperature of 40° C., and the tensile stress at break and Charpy impact strength were measured using the test piece.
• the results are shown in Table 1.
• the blending ratios of the carbon black master batch and the antioxidant were expressed as the blending ratio (phr) relative to 100 parts by mass of the total of the unmodified polypropylene resin (A-1), the acid-modified polypropylene resin (A-2), the phosphorus-based flame retardant (B), and the glass fiber (C).
• the amount of carbon black was expressed as the blending ratio (phr) relative to 100 parts by mass of the total of the polypropylene resin (A), the phosphorus-based flame retardant (B), and the glass fiber (C).
• the glass fiber-reinforced polypropylene resin composition of the present invention has excellent appearance and commercial value, and can be suitably used as a material for moldings with excellent mechanical properties in high-temperature, high-humidity environments in a variety of fields.

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