WO2022181010A1 - ガラス繊維強化プロピレン系樹脂組成物 - Google Patents

ガラス繊維強化プロピレン系樹脂組成物 Download PDF

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Publication number
WO2022181010A1
WO2022181010A1 PCT/JP2021/047045 JP2021047045W WO2022181010A1 WO 2022181010 A1 WO2022181010 A1 WO 2022181010A1 JP 2021047045 W JP2021047045 W JP 2021047045W WO 2022181010 A1 WO2022181010 A1 WO 2022181010A1
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Prior art keywords
glass fiber
propylene
mass
parts
resin composition
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PCT/JP2021/047045
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English (en)
French (fr)
Japanese (ja)
Inventor
成克 廣田
一之介 平野
義生 岡本
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Prime Polymer Co Ltd
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Prime Polymer Co Ltd
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Priority to EP21928103.7A priority Critical patent/EP4299666A4/en
Priority to JP2023502100A priority patent/JP7648733B2/ja
Priority to CN202180093260.6A priority patent/CN116829640B/zh
Priority to US18/277,207 priority patent/US20240141151A1/en
Publication of WO2022181010A1 publication Critical patent/WO2022181010A1/ja
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/10—Polymers of propylene
    • B29K2023/12—PP, i.e. polypropylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/10—Homopolymers or copolymers of propene
    • C08J2423/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

Definitions

  • the present invention relates to a glass fiber reinforced propylene resin composition.
  • Fiber-reinforced resin moldings are lightweight and have excellent rigidity and heat resistance, so they are used in various fields such as electrical equipment, automobiles, housing equipment, and medical equipment.
  • a fiber-reinforced resin molded article for example, a molded article using a reinforcing fiber such as glass fiber and a thermoplastic resin such as polyamide or polypropylene is known.
  • a thermoplastic resin such as polyamide or polypropylene is known.
  • such fiber-reinforced resin moldings are used for members that require high rigidity and heat resistance, such as fan shrouds and propeller fans in engine rooms.
  • Patent Document 1 describes a vehicle exterior part formed from a long glass fiber reinforced polyolefin composition containing long glass fiber reinforced polyolefin resin pellets, a polyolefin resin, an antioxidant, a light stabilizer, and an ultraviolet absorber. , describes that carbon black, wax, etc. can be further added to this composition.
  • Patent Document 2 describes a long glass fiber reinforced polyolefin composition containing long glass fiber reinforced polyolefin resin pellets, a polyolefin resin, and a pigment having zinc sulfide, and carbon black, wax, etc. are further added to this composition. It states what you can do.
  • Patent Document 3 describes a colorant composition containing an olefin resin, carbon black, and glass fiber, and further describes that polyethylene wax as a dispersant and lubricant can be added to this composition.
  • US Pat. No. 6,200,400 describes a composite material comprising a polymeric resin and glass fiber strands comprising glass fibers coated with an aqueous sizing composition disposed in said polymeric resin, wherein the sizing composition comprises carbon black, polypropylene It is described that wax or the like may be included.
  • Patent Document 5 describes a long-fiber-reinforced propylene-based resin composition containing an ethylene-based polymer having a density, melting point, and heat of fusion within predetermined ranges. It is described that it is possible to suppress the occurrence of appearance defects such as haze (hereinafter also referred to as "white haze”) and to form a molded article having excellent mechanical properties.
  • white haze appearance defects
  • Molded articles obtained from conventional glass fiber-reinforced propylene-based resin compositions have room for further improvement from the viewpoint of suppressing the generation of white haze.
  • the present inventors have found that white haze can be improved by adding carbon black to a glass fiber reinforced propylene resin composition and using a metal soap as a dispersant for carbon black. There was room for further improvement from the point of view of reducing the amount.
  • an object of the present invention is to provide a material suitable for manufacturing a glass fiber reinforced molded article that suppresses the occurrence of white haze while suppressing the amount of dispersant used.
  • the gist of the present invention is as follows. [1] 10 to 50 parts by mass of glass fiber, 50 to 90 parts by mass of propylene resin (where the total of glass fiber and propylene resin is 100 parts by mass), 0.3 parts by mass or more of carbon black, and a polyolefin wax having an average particle size of 1 to 40 ⁇ m in an amount such that the mass ratio of the polyolefin wax to the carbon black is 0.75 to 1.5.
  • a glass fiber reinforced propylene resin composition is as follows. [1] 10 to 50 parts by mass of glass fiber, 50 to 90 parts by mass of propylene resin (where the total of glass fiber and propylene resin is 100 parts by mass), 0.3 parts by mass or more of carbon black, and a polyolefin wax having an average particle size of 1 to 40 ⁇ m in an amount such that the mass ratio of the polyolefin wax to the carbon black is 0.75 to 1.5.
  • a method for manufacturing an injection-molded body comprising:
  • glass fiber-reinforced propylene-based resin composition of the present invention it is possible to produce a glass fiber-reinforced molded article that suppresses the occurrence of white haze while suppressing the amount of dispersant used.
  • the present invention will now be described in more detail.
  • the glass fiber-reinforced propylene-based resin composition according to the present invention is characterized by containing glass fibers, a propylene-based resin, carbon black, and a prescribed polyolefin wax.
  • the glass fiber-reinforced propylene-based resin composition of the present invention contains glass fibers.
  • glass fibers glass such as E glass (Electrical glass), C glass (Chemical glass), A glass (Alkali glass), S glass (High strength glass) and alkali-resistant glass are melt-spun into filament fibers. can be mentioned.
  • long glass fibers are usually used as glass fibers.
  • Continuous glass fiber bundles are usually used as raw materials for long glass fibers, and are commercially available as glass rovings.
  • the average fiber diameter is usually 3 to 30 ⁇ m, preferably 13 to 20 ⁇ m, more preferably 16 to 18 ⁇ m, and the number of filament bundles is usually 400 to 10,000, preferably 1,000 to 6,000, More preferably, it is 3,000 to 5,000.
  • a plurality of fiber bundles can be bundled and used.
  • Functional groups may be introduced onto the surface of the glass fiber by various surface treatment methods such as electrolytic treatment or sizing agent treatment. It is preferable to use a sizing agent for the surface treatment, and it is particularly preferable to use a sizing agent containing a coupling agent.
  • a sizing agent for the surface treatment it is particularly preferable to use a sizing agent containing a coupling agent.
  • Examples of sizing agents include those containing coupling agents described in JP-A-2003-253563.
  • Examples of coupling agents include silane-based coupling agents such as aminosilane and epoxysilane, and titanium-based coupling agents.
  • the sizing agent preferably contains a resin emulsion in order to facilitate handling.
  • the resin emulsion contained in the sizing agent include urethane, olefin, acrylic, nylon, butadiene, and epoxy emulsions, and of these, urethane and olefin emulsions are preferred.
  • the glass fiber-reinforced propylene-based resin composition of the present invention contains a propylene-based resin.
  • the propylene-based resin is a polymer containing propylene-derived structural units as main structural units, and examples thereof include propylene homopolymers, propylene/ ⁇ -olefin random copolymers, and propylene-based block copolymers (hereinafter , which are collectively referred to as “unmodified propylene-based resins”), and modified polypropylene.
  • the propylene/ ⁇ -olefin random copolymer is a random copolymer of propylene and at least one olefin selected from ⁇ -olefins having 2 carbon atoms (ie, ethylene) and ⁇ -olefins having 4 to 8 carbon atoms. coalescence is mentioned.
  • ⁇ -olefins include ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene and 1-octene, Ethylene and 1-butene are preferred, and ethylene is particularly preferred.
  • the ratio of propylene-derived structural units to all structural units in the random copolymer is preferably 90 mol % or more, more preferably 95 mol % or more.
  • the propylene-based block copolymer is preferably composed of a propylene homopolymer portion and a propylene/ ⁇ -olefin random copolymer portion. Specific aspects of the propylene/ ⁇ -olefin random copolymer portion are the same as those of the propylene/ ⁇ -olefin random copolymer.
  • the propylene-based block copolymer When the propylene-based block copolymer is fractionated with an n-decane solvent, there are component (hereinafter also referred to as “decane-insoluble portion”).
  • the content of the decane soluble part is usually 5 to 30% by mass, preferably 5 to 25% by mass, more preferably 8 to 18% by mass, and the content of the decane insoluble part is usually 70 to 95% by mass. %, preferably 75 to 95 mass %, more preferably 82 to 92 mass %.
  • the modified polypropylene is obtained by acid-modifying polypropylene. Modification methods include conventionally known methods such as graft modification and copolymerization.
  • the polypropylene to be modified includes the unmodified propylene-based resin.
  • Modifiers used for modification include, for example, unsaturated carboxylic acids and derivatives thereof.
  • unsaturated carboxylic acids include acrylic acid, methacrylic acid, maleic acid, nadic acid, fumaric acid, itaconic acid, crotonic acid, citraconic acid, sorbic acid, mesaconic acid, angelic acid, and phthalic acid.
  • derivatives thereof include acid anhydrides, esters, amides, imides, and metal salts. Specific examples include maleic anhydride, itaconic anhydride, citraconic anhydride, nadic anhydride, and phthalic anhydride.
  • the acid addition amount of the modified polypropylene in other words, the ratio of the structure derived from the acid in the modified polypropylene is preferably 0.1 to 14% by weight, more preferably 0.3 to 8% by weight.
  • the amount of acid addition is determined from the area of the peak from 1,670 cm -1 to 1,810 cm -1 by measuring the IR spectrum of the resin.
  • the polypropylene may be modified prior to the production of the glass fiber reinforced resin pellets. It may be performed in the actual melt-kneading process.
  • a modifier or a volatile component derived therefrom (hereinafter collectively referred to as a "volatile component”) remains in the modified polypropylene, the glass fiber-reinforced propylene-based resin composition is formed. Clouding may occur on the surface of the molded product. Therefore, it is preferable that the volatile component is small, and the volatile component content in the modified polypropylene, defined by the formula described in [0039] of WO 2020/091051, is preferably 9000 ppm or less, more preferably 7000 ppm or less. The amount of volatile components can be reduced by, for example, vacuum drying the modified polypropylene.
  • modified polypropylene from the viewpoint of improving the affinity between the glass fiber and the unmodified propylene-based polymer and improving the strength or heat resistance of the molded article to be produced, fatty acid anhydride-modified polypropylene is preferable, particularly maleic anhydride. Modified polypropylene is preferred.
  • the melt flow rate of modified polypropylene (according to ISO 1133-1, 230°C, 2.16 kg load) is preferably 50 g/10 minutes or more, more preferably 80 g/10 minutes or more, and the upper limit thereof is, for example, It may be 1000 g/10 minutes.
  • the glass fiber-reinforced propylene-based resin composition of the present invention has fluidity suitable for injection molding.
  • melt flow rate of the propylene-based resin as a whole is , preferably 25 to 500 g/10 min, more preferably 50 to 400 g/10 min.
  • Glass fiber reinforced resin pellets In the glass fiber-reinforced propylene-based resin composition of the present invention, part or all of the propylene-based resin (hereinafter also referred to as “propylene-based resin (P1)”) and the glass fibers are pellets (hereinafter referred to as “glass fiber (also referred to as “reinforced resin pellets”) may be formed.
  • P1 propylene-based resin
  • glass fiber also referred to as “reinforced resin pellets
  • the melt flow rate of the unmodified propylene-based resin is preferably 20 g/10 minutes or more, more It is preferably 30 g/10 minutes or more, more preferably 40 g/10 minutes or more, and its upper limit may be, for example, 300 g/10 minutes.
  • the melt flow rate is within this range, the composition of the present invention has fluidity suitable for injection molding.
  • the fiber length of the glass fiber in the glass fiber reinforced resin pellet is usually 4-10 mm, preferably 5-8 mm, and the fiber diameter is usually 10-20 ⁇ m, preferably 13-18 ⁇ m.
  • the glass fibers are arranged substantially parallel to the longitudinal direction of the pellet, and the fiber length of the glass fiber is generally substantially equal to the particle length of the pellet (that is, the length in the longitudinal direction of the pellet). are essentially identical.
  • the content of glass fiber in the glass fiber reinforced resin pellet is preferably 40-70% by mass, more preferably 45-60% by mass, based on 100% by mass of the glass fiber reinforced resin pellet.
  • glass fiber reinforced resin pellets can be produced with good productivity.
  • the content of the glass fiber is equal to or less than the upper limit, the fiber bundle of the glass fiber can be sufficiently impregnated with the resin.
  • the amount of modified polypropylene in the glass fiber reinforced resin pellets is preferably 1 to 5% by mass, more preferably 1.5 to 3.5% by mass, relative to 100% by mass of the glass fiber reinforced resin pellets.
  • the amount of the modified polypropylene is at least the lower limit, the adhesion between the glass fiber and the resin component is good.
  • the amount of the modified polypropylene is equal to or less than the upper limit, the strength of the molded article produced from the composition of the present invention is good because the molecular weight of the modified polypropylene does not become too low.
  • the shape of glass fiber reinforced resin pellets is generally columnar.
  • the particle length (longitudinal length) of the glass fiber reinforced resin pellets is usually 4 to 10 mm, preferably 5 to 8 mm.
  • the molded article produced from the glass fiber-reinforced propylene-based resin composition of the present invention has excellent mechanical properties.
  • the particle length of the glass fiber-reinforced resin pellets is equal to or less than the upper limit, the glass fiber-reinforced propylene-based resin composition of the present invention is excellent in moldability.
  • glass fibers are usually arranged substantially parallel to the longitudinal direction of the pellet. Since the aspect ratio of the glass fiber in the glass fiber-reinforced resin pellets is large, the molded article formed from the glass fiber-reinforced propylene-based resin composition of the present invention containing the glass fiber-reinforced resin pellets has excellent mechanical strength.
  • Glass fiber reinforced resin pellets can be produced by a known molding method such as a drawing method. It may be simply referred to as "molten resin” below.) is evenly impregnated between the filaments and then cut to the required length.
  • a molten resin is supplied from the extruder into an impregnation die provided at the tip of the extruder, while a continuous glass fiber bundle is passed through, and the glass fiber bundle is impregnated with the molten resin. It is drawn through a nozzle and pelletized to the required length.
  • the unmodified propylene-based polymer, the unsaturated carboxylic acid or its anhydride can be dry-blended together with the organic peroxide, put into the hopper of the extruder, and supplied while being modified at the same time.
  • the method for impregnating the glass fiber roving with the molten resin is not particularly limited, and includes, for example, the method described in [0036] of International Publication 2010/137305.
  • an extruder having two or more feed parts may be used, and the resin and decomposing agent may be fed from the top feed and another resin may be fed from the side feed.
  • Organic peroxides are preferred as the decomposing agent.
  • two or more extruders (extrusion units) may be used, and the decomposing agent may be introduced into at least one of them.
  • the resin, the unsaturated carboxylic acid or its derivative and the decomposing agent may be introduced into at least one portion of the extruder.
  • the propylene-based resin (P2) is a polymer containing propylene-derived structural units as main structural units. Examples thereof include propylene homopolymers, propylene/ ⁇ -olefin random copolymers, and propylene-based block copolymers. coalescence is mentioned.
  • the melt flow rate of the propylene-based resin (P2) (according to ISO 1133-1, 230°C, 2.16 kg load) is preferably 10 to 300 g/10 minutes, more preferably 20 to 250 g/10 minutes, still more preferably 20 to 200 g/10 minutes.
  • the melt flow rate of the propylene-based resin (P2) is within this range, the molded article formed from the glass fiber-reinforced propylene-based resin composition of the present invention has excellent mechanical properties.
  • Examples of the shape of the propylene-based resin (P2) include powder and pellets.
  • Carbon black The glass fiber-reinforced propylene-based resin composition of the present invention contains carbon black.
  • the content of carbon black in the composition of the present invention is 0.3 parts by mass or more, preferably 0.3 to 2 parts by mass with respect to 100 parts by mass in total of the glass fiber and the propylene-based resin. .
  • the carbon black content is within the above range, white haze is suppressed in the reinforcing fiber molded article produced from the glass fiber-reinforced propylene-based resin composition.
  • the content is less than 0.3 parts by mass, the occurrence of white haze may not be suppressed.
  • the content is equal to or less than the upper limit, the interfacial adhesion between the glass reinforcing fiber and the propylene-based resin is good.
  • the glass fiber-reinforced propylene-based resin composition of the present invention contains polyolefin wax having an average particle size of 1 to 40 ⁇ m, preferably 5 to 20 ⁇ m. This average particle size is the D50 in the volume-based particle size distribution measured by laser diffraction.
  • the average particle size of the polyolefin wax is within this range, the polyolefin wax is effectively arranged between the carbon black particles to prevent aggregation of the carbon black particles and improve the dispersibility of the carbon black in the resin component. It is possible to suppress the occurrence of white haze in the molded body. On the other hand, if the average particle diameter is too much smaller than the lower limit, it may be difficult to produce the polyolefin wax. It may not be possible to suppress the generation of white haze in the molded product.
  • the mechanical properties of the molded article tend to decrease as the amount of the ethylene-based polymer increases.
  • the occurrence of white haze is suppressed by blending carbon black and polyolefin wax, so it is expected that there will be no concern when blending the above-mentioned ethylene polymer. .
  • the polystyrene-equivalent number-average molecular weight (Mn) of the polyolefin wax measured by gel permeation chromatography (GPC) under the following or equivalent conditions is preferably 2,000 to 10,000, more preferably 3,000, 000 to 4,000.
  • Apparatus Gel permeation chromatograph Alliance GPC2000 type (manufactured by Waters) Solvent: o-dichlorobenzene Column: TSKgel GMH6-HT ⁇ 2, TSKgel GMH6-HTL column ⁇ 2 (both manufactured by Tosoh Corporation) Flow rate: 1.0 ml/min Sample: 0.15 mg/mL o-dichlorobenzene solution Temperature: 140°C The mass ratio of polyolefin wax to carbon black (mass of polyolefin wax/mass of carbon black) is 0.75 to 1.5, preferably 0.80 to 1.0.
  • the polyolefin wax can be effectively arranged between the carbon black particles to prevent aggregation of the carbon black particles and improve the dispersibility of the carbon black in the resin component. Therefore, it is possible to suppress the occurrence of white haze in the molded product.
  • the mass ratio is too much smaller than the lower limit, the dispersibility of carbon black is low, and it may not be possible to suppress the occurrence of white haze in the molded article.
  • polyethylene wax and polypropylene wax are preferable, and polypropylene wax is more preferable.
  • Polyolefin waxes may be used singly or in combination of two or more.
  • the glass fiber-reinforced propylene-based resin composition of the present invention may, if necessary, contain polymers other than the respective components described above within a range that does not impair the effects of the present invention.
  • polymers include ethylene-based polymers, and examples of ethylene-based polymers are ethylene-based polymers described in paragraphs [0054] to [0060] of WO 2020/091051. is mentioned.
  • the glass fiber-reinforced propylene-based resin composition of the present invention may optionally contain a heat stabilizer, an antistatic agent, a weather stabilizer, a light stabilizer, an anti-aging agent, an antioxidant, and copper.
  • Additives such as harm inhibitors, fatty acid metal salts, softeners, dispersants (except for the polyolefin waxes), fillers, colorants, pigments, foaming agents, etc., are used within a range that does not impair the effects of the present invention (for example, (at a ratio of 5% by mass or less with respect to 100% by mass of the composition).
  • These components may be masterbatched.
  • the glass fiber reinforced propylene resin composition of the present invention is 10 to 50 parts by mass, preferably 15 to 45 parts by mass, more preferably 20 to 40 parts by mass of the glass fiber; 50 to 90 parts by mass, preferably 55 to 85 parts by mass, more preferably 60 to 80 parts by mass of the propylene resin (where the total of the glass fiber and the propylene resin is 100 parts by mass); 0.3 parts by mass or more of the carbon black, preferably 0.3 to 2 parts by mass; It is contained in an amount of 80 to 1.0.
  • the glass fiber-reinforced propylene-based resin composition of the present invention is, for example, dry-blended by mixing the glass fiber, the propylene-based resin, the carbon black, the polyolefin wax, and optionally the additive. It can be manufactured by
  • the glass fiber-reinforced molded article according to the present invention comprises a composition containing the glass fiber, the propylene-based resin, the carbon black, the polyolefin wax, and optionally the additive.
  • each component is as described above unless otherwise specified.
  • the content of each component in the composition and its technical significance are the content of each component in the glass fiber-reinforced propylene-based resin composition according to the present invention described above and its technical significance. Same as meaning.
  • the length of the glass fibers in the molded article of the present invention is usually different from the length of the glass fibers in the glass fiber-reinforced propylene-based resin composition of the present invention. This is because the glass fibers are broken and shortened during molding.
  • the length of the glass fiber in the glass fiber reinforced molded article according to the present invention is calculated based on the following formula by extracting a predetermined number (1000) of glass fibers from the molded article, measuring the length of each fiber.
  • the weight average fiber length is usually 0.5 to 5 mm, preferably 0.8 to 3 mm.
  • the glass fiber reinforced molding according to the present invention comprises the glass fiber, the propylene resin, the carbon black, the polyolefin wax, and optionally the It can be produced by molding a resin composition containing additives, for example, the glass fiber-reinforced propylene-based resin composition according to the present invention described above.
  • injection molding method known molding methods such as injection molding method, extrusion molding method, blow molding method, compression molding method, injection compression molding method, gas injection injection molding and foam injection molding can be applied without particular limitation.
  • injection molding, compression molding, and injection compression molding are particularly preferable, and injection molding is preferable from the viewpoint of producing molded articles with excellent appearance (that is, the generation of white haze is suppressed).
  • the molded product of the present invention can be suitably used in various fields such as automotive interior and exterior parts, home appliance parts, and the like.
  • automotive interior and exterior parts include back door inner materials.
  • melt flow rate The melt flow rate of the starting resin was measured under conditions of 230° C. and a load of 2.16 kg according to ISO 1133-1.
  • Average particle size As the average particle size of the dispersant, D50 in volume-based particle size distribution measured by laser diffraction method was employed.
  • 10 is a die
  • 20 is an extruder that supplies molten resin to the die
  • 30 is a roll for the fiber bundle F
  • 40 is a group of tension rolls that apply a constant tension to the fiber bundle F drawn into the die 10
  • 50 is a cooling means for cooling the molten resin-impregnated fiber bundle pulled out from the die
  • 60 is a pull-out roll for the fiber bundle
  • 70 is a pelletizer for cutting the pulled-out molten resin-impregnated fiber bundle.
  • three independent fiber bundles F are simultaneously impregnated with molten resin.
  • a molded body (color plate) was produced from this glass fiber reinforced resin composition using an injection molding machine under the following conditions, and its appearance was evaluated.
  • Mold 90 mm x 50 mm x 2 mm, with embossed depth of 15 ⁇ m Molding temperature: 240 ° C Mold temperature: 45°C Table 1 shows the evaluation results.
  • Comparative Example 2 A glass fiber reinforced resin composition and a molded article thereof were produced in the same manner as in Comparative Example 1, except that 0.2 parts by mass of calcium stearate was changed to 0.2 parts by mass of polypropylene wax. Table 1 shows the evaluation results.
  • Comparative Example 3 A glass fiber reinforced resin composition and a molded article thereof were produced in the same manner as in Comparative Example 1, except that 0.2 parts by mass of calcium stearate was changed to 0.2 parts by mass of micronized polypropylene wax. Table 1 shows the evaluation results.
  • Comparative Example 4 A glass fiber reinforced resin composition and a molded article thereof were prepared in the same manner as in Comparative Example 1 except that the amount of carbon black was changed to 0.4 parts by mass and the amount of calcium stearate was changed to 0.4 parts by mass. manufactured. Table 1 shows the evaluation results.
  • Comparative Example 5 A glass fiber reinforced resin composition and a molded article thereof were prepared in the same manner as in Comparative Example 2 except that the amount of carbon black was changed to 0.4 parts by mass and the amount of polypropylene wax was changed to 0.4 parts by mass. manufactured. Table 1 shows the evaluation results.
  • Example 1 Glass fiber A reinforced resin composition and a molded article thereof were produced. Table 1 shows the evaluation results.
  • Comparative Example 6 A glass fiber reinforced resin composition and a molded article thereof were prepared in the same manner as in Comparative Example 1 except that the amount of carbon black was changed to 0.8 parts by mass and the amount of calcium stearate was changed to 0.8 parts by mass. manufactured. Table 1 shows the evaluation results.
  • Comparative Example 7 A glass fiber reinforced resin composition and a molded article thereof were prepared in the same manner as in Comparative Example 2 except that the amount of carbon black was changed to 0.8 parts by mass and the amount of polypropylene wax was changed to 0.8 parts by mass. manufactured. Table 1 shows the evaluation results.
  • Example 2 A glass fiber reinforced resin composition and its A molded body was produced. Table 1 shows the evaluation results.
  • Comparative Example 8 A glass fiber reinforced resin composition and a molded article thereof were prepared in the same manner as in Comparative Example 1 except that the amount of carbon black was changed to 1.2 parts by mass and the amount of calcium stearate was changed to 1.2 parts by mass. manufactured. Table 1 shows the evaluation results.
  • Comparative Example 9 A glass fiber reinforced resin composition and a molded article thereof were prepared in the same manner as in Comparative Example 2 except that the amount of carbon black was changed to 1.2 parts by mass and the amount of polypropylene wax was changed to 1.2 parts by mass. manufactured. Table 1 shows the evaluation results.
  • Example 3 A glass fiber reinforced resin composition and its A molded body was produced. Table 1 shows the evaluation results.
  • Comparative Example 10 A glass fiber reinforced resin composition and a molded article thereof were prepared in the same manner as in Comparative Example 1 except that the amount of carbon black was changed to 1.6 parts by mass and the amount of calcium stearate was changed to 1.6 parts by mass. manufactured. Table 1 shows the evaluation results.
  • Comparative Example 11 A glass fiber reinforced resin composition and a molded article thereof were prepared in the same manner as in Comparative Example 2 except that the amount of carbon black was changed to 1.6 parts by mass and the amount of polypropylene wax was changed to 1.6 parts by mass. manufactured. Table 1 shows the evaluation results.
  • Example 4 A glass fiber reinforced resin composition and its A molded body was produced. Table 1 shows the evaluation results.

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  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
PCT/JP2021/047045 2021-02-25 2021-12-20 ガラス繊維強化プロピレン系樹脂組成物 Ceased WO2022181010A1 (ja)

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EP21928103.7A EP4299666A4 (en) 2021-02-25 2021-12-20 PROPYLENE-BASED RESIN COMPOSITION, REINFORCED BY GLASS FIBERS
JP2023502100A JP7648733B2 (ja) 2021-02-25 2021-12-20 ガラス繊維強化プロピレン系樹脂組成物
CN202180093260.6A CN116829640B (zh) 2021-02-25 2021-12-20 玻璃纤维强化丙烯系树脂组合物
US18/277,207 US20240141151A1 (en) 2021-02-25 2021-12-20 Glass fiber-reinforced propylene-based resin composition

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