Glass fiber reinforced propylene resin composition

Abstract

[Problem] To provide a material suitable for the production of a glass fiber-reinforced molded article which has excellent mechanical properties, and in which adjustment of color tone is easy and occurrence of white blurring is suppressed. [Solution] This glass fiber-reinforced propylene-based resin composition contains: 10-50 parts by mass of glass fibers; 50-90 parts by mass of a propylene-based resin (when the total of the glass fiber and the propylene-based resin is defined as 100 parts by mass); 0.12 parts by mass or more of carbon black; a polyolefin wax having an average particle diameter of 1-40 μm, in an amount where the mass ratio of the polyolefin wax with respect to the carbon black is 0.75-2.0; and more than 0 parts by mass but not more than 1.3 parts by mass of zinc sulfide.

Description

[Technical Field]

[0001] The present invention relates to a glass fiber reinforced propylene resin composition. [Background technology]

[0002] Fiber-reinforced resin moldings are lightweight and have excellent rigidity and heat resistance, and are therefore used in a wide variety of fields, including electrical equipment, automobiles, housing equipment, and medical instruments.

[0003] Known examples of fiber-reinforced resin moldings include moldings made of reinforcing fibers such as glass fibers and thermoplastic resins such as polyamide and polypropylene. Such fiber-reinforced resin moldings are used in the automotive field for components that require high rigidity and heat resistance, such as fan shrouds and propeller fans in engine compartments.

[0004] For example, 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, and also 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 containing zinc sulfide, and also describes that carbon black, wax, etc. can be further added to this composition.

[0005] Patent Document 3 describes a colorant composition containing an olefin resin, carbon black, and glass fiber, and also describes that polyethylene wax can be further added to this composition as a dispersant and a lubricant.

[0006] Patent Document 4 describes a composite material including a polymer resin and glass fiber strands that include glass fibers coated with an aqueous sizing composition disposed in the polymer resin, and describes that the sizing composition may include carbon black, polypropylene wax, etc.

[0007] On the other hand, 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 a predetermined range, and describes that this composition can be used to form a molded body that is free from poor appearance such as a white haze on the surface of the molded body (hereinafter also referred to as "occurrence of white haze") and has excellent mechanical properties. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Japanese Patent Application Publication No. 9-207233 [Patent Document 2] Japanese Patent Application Publication No. 9-183869 [Patent Document 3] Japanese Patent Application Laid-Open No. 2002-53711 [Patent Document 4] Special Publication No. 2014-512323 [Patent Document 5] International Publication No. 2020 / 091051 Summary of the Invention [Problem to be solved by the invention]

[0009] Molded articles obtained from conventional glass fiber reinforced propylene-based resin compositions have room for further improvement in terms of suppressing the occurrence of haze.

[0010] The present inventors have found that the generation of white haze can be suppressed by blending carbon black and polyolefin wax into a glass fiber reinforced propylene resin composition, but the blending of carbon black makes the color tone of the molded product too dark, making it difficult to adjust the color tone, and blending a white pigment to solve this color tone problem can sometimes result in a deterioration in the mechanical properties of the molded product. Furthermore, when the molded product is large, the generation of white haze cannot always be suppressed sufficiently.

[0011] Therefore, an object of the present invention is to provide a material suitable for producing a glass fiber reinforced molding that is suppressed from generating haze, is easy to adjust the color tone, and has excellent mechanical properties. Another object of the present invention is to provide a material that is suitable for sufficiently suppressing the generation of haze even when the molding is large. [Means for solving the problem]

[0012] The gist of the present invention is as follows.

[0013] [1] 10 to 50 parts by mass of glass fiber, 50 to 90 parts by mass of propylene-based resin (where the total of the glass fiber and the propylene-based resin is 100 parts by mass), 0.12 parts by mass or more of carbon black, a polyolefin wax having an average particle size of 1 to 40 μm in an amount such that the mass ratio of the polyolefin wax to the carbon black is 0.75 to 2.0; and Contains more than 0 parts by mass and 1.3 parts by mass or less of zinc sulfide, Glass fiber reinforced propylene resin composition.

[0014] [2] The glass fiber-reinforced propylene resin composition according to [1], wherein the content of the glass fiber is 25 to 50 parts by mass.

[0015] [3] The glass fiber reinforced propylene resin composition according to [1] or [2] above, wherein the polyolefin wax is a polypropylene wax. [Effects of the Invention]

[0016] The glass fiber-reinforced propylene-based resin composition of the present invention can suppress the generation of white haze, facilitate color adjustment, and produce a glass fiber-reinforced molded article with excellent mechanical properties. Furthermore, the glass fiber-reinforced propylene-based resin composition of the present invention can provide a material suitable for sufficiently suppressing the generation of white haze even when the molded article is large. [Brief explanation of the drawings]

[0017] [Figure 1] FIG. 1 is a schematic diagram of a pellet manufacturing apparatus. DETAILED DESCRIPTION OF THE INVENTION

[0018] The present invention will now be described in further detail.

[0019] [Glass fiber reinforced propylene resin composition] The glass fiber reinforced propylene resin composition according to the present invention is characterized by containing glass fiber, a propylene resin, carbon black, a polyolefin wax, and zinc sulfide.

[0020] Glass fiber The glass fiber reinforced propylene resin composition of the present invention contains glass fibers.

[0021] Examples of glass fibers include filament-like fibers obtained by melt-spinning glass such as E-glass (electrical glass), C-glass (chemical glass), A-glass (alkaline glass), S-glass (high strength glass), and alkali-resistant glass.

[0022] In the present invention, long glass fibers are usually used as the glass fibers. Continuous glass fiber bundles are usually used as the raw material for the long glass fibers, and are commercially available as glass rovings. The average fiber diameter is usually 3 to 30 μm, preferably 13 to 20 μm, and more preferably 16 to 18 μm, and the number of filaments in the bundle is usually 400 to 10,000, preferably 1,000 to 6,000, and more preferably 3,000 to 5,000.

[0023] Furthermore, as described in Japanese Patent Application Laid-Open No. 6-114830, a plurality of fiber bundles may be bundled together and used.

[0024] Functional groups may be introduced onto the surface of the glass fiber by various surface treatment methods such as electrolytic treatment or treatment with a sizing agent. The surface treatment is preferably carried out using a sizing agent, and it is particularly preferable to use a sizing agent containing a coupling agent. The use of surface-treated glass fiber improves the adhesion between the glass fiber and the resin component, resulting in a molded product with good strength and appearance.

[0025] Examples of the sizing agent include those containing a coupling agent as described in JP-A-2003-253563.

[0026] Examples of the coupling agent include silane-based coupling agents such as aminosilane and epoxysilane, and titanium-based coupling agents.

[0027] In addition to the coupling agent, the binder preferably contains a resin emulsion for ease of handling.

[0028] Examples of resin emulsions contained in the sizing agent include urethane-based, olefin-based, acrylic-based, nylon-based, butadiene-based, and epoxy-based emulsions, and among these, urethane-based and olefin-based emulsions are preferred.

[0029] <Propylene-based resin> The glass fiber reinforced propylene-based resin composition of the present invention contains a propylene-based resin.

[0030] The propylene-based resin is a polymer containing propylene-derived structural units as the main structural unit, and examples thereof include propylene homopolymer, propylene-α-olefin random copolymer, propylene-based block copolymer (hereinafter, these are also collectively referred to as "unmodified propylene-based resin"), and modified polypropylene.

[0031] The propylene-α-olefin random copolymer may be a random copolymer of propylene with at least one olefin selected from ethylene and α-olefins having 4 to 8 carbon atoms. Examples of the α-olefin include ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, and 1-octene, preferably ethylene and 1-butene, and particularly preferably ethylene. The proportion of propylene-derived structural units in all structural units in the random copolymer is preferably 90 mol% or more, more preferably 95 mol% or more.

[0032] The propylene-based block copolymer preferably comprises a propylene homopolymer portion and a propylene-α-olefin random copolymer portion, and the specific embodiments of the propylene-α-olefin random copolymer portion are the same as those of the propylene-α-olefin random copolymer.

[0033] When the propylene-based block copolymer is fractionated with an n-decane solvent, it is separated into a component soluble in n-decane at 23° C. (hereinafter also referred to as the "decane-soluble portion") and a component insoluble in n-decane at 23° C. (hereinafter also referred to as the "decane-insoluble portion") The content of the decane-soluble portion is usually 5 to 30 mass%, preferably 5 to 25 mass%, and more preferably 8 to 18 mass%, and the content of the decane-insoluble portion is usually 70 to 95 mass%, preferably 75 to 95 mass%, and more preferably 82 to 92 mass%.

[0034] The modified polypropylene can be obtained by acid-modifying polypropylene. The modification method includes conventionally known methods such as graft modification and copolymerization. The modified polypropylene can be the unmodified propylene resin.

[0035] Examples of modifiers used for modification include unsaturated carboxylic acids and their derivatives. Examples of 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. Examples of derivatives thereof include acid anhydrides, esters, amides, imides, and metal salts. Specific examples include maleic anhydride, itaconic anhydride, citraconic anhydride, nadic anhydride, phthalic anhydride, methyl acrylate, methyl methacrylate, ethyl acrylate, butyl acrylate, maleic acid monoethyl ester, acrylamide, maleic acid monoamide, maleimide, N-butylmaleimide, sodium acrylate, and sodium methacrylate. Among these, unsaturated dicarboxylic acids and their derivatives are preferred, with maleic anhydride and phthalic anhydride being more preferred.

[0036] The amount of acid added to the modified polypropylene, in other words, the proportion 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 added is measured by measuring the IR spectrum of the resin and determining the peak at 1,670 cm -1 ~1,810cm -1 It is determined from the area of ​​the peak.

[0037] When the glass fiber and the propylene-based resin form glass fiber reinforced resin pellets as described below, the modification of the polypropylene may be carried out prior to the production of the glass fiber reinforced resin pellets, or may be carried out during the melt-kneading process in the production of the glass fiber reinforced resin pellets.

[0038] If the modified polypropylene contains a modifier or volatile components derived therefrom (hereinafter, these are also collectively referred to as "volatile components"), cloudiness may occur on the surface of a molded article formed from the glass fiber reinforced propylene resin composition. For this reason, it is preferable that the amount of the volatile components is small.

[0039] The content of volatile components in the modified polypropylene, as defined by the formula shown below, is preferably 9000 ppm or less, more preferably 7000 ppm or less. The amount of volatile components can be reduced by vacuum drying the modified polypropylene, for example.

[0039] As the modified polypropylene, from the viewpoint of improving the affinity between the glass fiber and the unmodified propylene polymer and improving the strength or heat resistance of the molded article to be produced, fatty acid anhydride-modified polypropylene is preferred, and maleic anhydride-modified polypropylene is particularly preferred.

[0040] The melt flow rate of the modified polypropylene (according to ISO 1133-1, 230°C, 2.16 kg load) is preferably 50 g / 10 min or more, more preferably 80 g / 10 min or more, and the upper limit may be, for example, 1000 g / 10 min. When the melt flow rate of the modified polypropylene is within this range, the glass fiber-reinforced propylene resin composition of the present invention has fluidity suitable for injection molding.

[0041] The melt flow rate of the propylene-based resin as a whole (according to ISO 1133-1, 230°C, 2.16 kg load) is preferably 25 to 500 g / 10 min, more preferably 50 to 400 g / 10 min, from the viewpoint of injection molding a molded article having excellent mechanical properties with good processability. The propylene-based resin may contain structural units derived from biomass-derived propylene. The propylene constituting the polymer may be only biomass-derived propylene, only fossil fuel-derived propylene, or both biomass-derived propylene and fossil fuel-derived propylene. Biomass-derived propylene is propylene obtained from any renewable natural raw material, such as a plant-derived or animal-derived material, including fungi, yeast, algae, and bacteria, and its residues, and contains propylene as carbon. 14 C isotope 1×10 -12 The biomass carbon concentration (pMC) measured in accordance with ASTM D 6866 is about 100 (pMC). Biomass-derived propylene can be obtained, for example, by a conventionally known method.

[0042] It is preferable that the propylene-based resin contains structural units derived from biomass-derived propylene from the viewpoint of reducing environmental load (mainly greenhouse gas reduction). If the polymer production conditions such as the polymerization catalyst, polymerization process, and polymerization temperature are the same, even if the raw material propylene is a propylene-based polymer containing biomass-derived propylene, 14 C isotope 1×10 -12 Other than the proportion of propylene in the polymer, its molecular structure is the same as that of propylene homopolymer, which is made from fossil fuel-derived propylene. Therefore, its performance is said to be the same. The propylene-based resin may contain structural units derived from chemically recycled propylene. The propylene constituting the polymer may be solely chemically recycled propylene, or may contain chemically recycled propylene and fossil fuel-derived propylene and / or biomass-derived propylene. Chemically recycled propylene can be obtained, for example, by a conventionally known method.

[0043] It is preferable that the propylene-based resin contains structural units derived from chemically recycled propylene from the viewpoint of reducing environmental impact (mainly waste reduction). Even if the raw material monomer is a propylene-based polymer containing a chemically recycled monomer, the chemically recycled monomer is a monomer obtained by depolymerizing or thermally decomposing a polymer such as waste plastics to return it to a monomer unit such as propylene, or a monomer produced using such a monomer as a raw material. Therefore, if the polymer production conditions, such as the polymerization catalyst, polymerization process, and polymerization temperature, are equivalent, the molecular structure is equivalent to that of a propylene homopolymer made from a fossil fuel-derived monomer. Therefore, the performance is also said to be unchanged. (glass fiber reinforced resin pellets) In the glass fiber reinforced propylene-based resin composition of the present invention, a part or all of the propylene-based resin (hereinafter also referred to as "propylene-based resin (P1)") and the glass fibers may be in the form of pellets (hereinafter also referred to as "glass fiber reinforced resin pellets").

[0044] The unmodified propylene resin (P1) contained in the pellets preferably has a melt flow rate (according to ISO 1133-1, 230°C, 2.16 kg load) of 20 g / 10 min or more, more preferably 30 g / 10 min or more, and even more preferably 40 g / 10 min or more, and the upper limit may be, for example, 300 g / 10 min. When the melt flow rate is in this range, the composition of the present invention has fluidity suitable for injection molding.

[0045] The fiber length of the glass fibers in the glass fiber reinforced resin pellets is usually 4 to 10 mm, preferably 5 to 8 mm, and the fiber diameter is usually 10 to 20 μm, preferably 13 to 18 μm.

[0046] In a glass fiber reinforced resin pellet, the glass fibers are aligned approximately parallel to the longitudinal direction of the pellet, and the fiber length of the glass fibers is usually substantially the same as the particle length of the pellet (i.e., the length of the pellet in the longitudinal direction).

[0047] The content of glass fibers in the glass fiber reinforced resin pellets is preferably 40 to 70% by mass, more preferably 45 to 60% by mass, based on 100% by mass of the glass fiber reinforced resin pellets. When the content of glass fibers is equal to or greater than the lower limit, the glass fiber reinforced resin pellets can be produced with good productivity. When the content of glass fibers is equal to or less than the upper limit, the glass fiber bundles can be sufficiently impregnated with the resin.

[0048] The amount of modified polypropylene in the glass fiber reinforced resin pellets is preferably 1 to 5 mass %, more preferably 2 to 5 mass %, based on 100 mass % of the glass fiber reinforced resin pellets. When the amount of modified polypropylene is equal to or greater than the lower limit, the adhesion between the glass fibers and the resin component is good. When the amount of modified polypropylene is equal to or less than the upper limit, the molecular weight of the modified polypropylene does not become too low, and therefore, the strength of the molded article produced from the composition of the present invention is good.

[0049] The shape of the glass fiber reinforced resin pellets is usually columnar.

[0050] The particle length (length in the longitudinal direction) of the glass fiber reinforced resin pellets is usually 4 to 10 mm, preferably 5 to 8 mm. When the particle length of the glass fiber reinforced resin pellets is equal to or greater than the lower limit, the molded article produced from the glass fiber reinforced propylene-based resin composition of the present invention has excellent mechanical properties. When 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 has excellent moldability.

[0051] In glass fiber reinforced resin pellets, the glass fibers are usually aligned approximately parallel to the longitudinal direction of the pellets.

[0052] Since the aspect ratio of the glass fibers in the glass fiber reinforced resin pellets is large, a molded article formed from the glass fiber reinforced propylene resin composition of the present invention containing the glass fiber reinforced resin pellets has excellent mechanical strength.

[0053] Glass fiber reinforced resin pellets can be produced by a known molding method such as a drawing method. Specifically, the glass fiber reinforced resin pellets can be easily obtained by introducing a roving of several thousand glass fibers into an impregnation die, uniformly impregnating the spaces between the filaments with molten propylene-based resin (hereinafter also simply referred to as "molten resin"), and then cutting the pellets to the required length.

[0054] In this method, for example, 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 the extruder. After the glass fiber bundle is impregnated with the molten resin, the bundle is drawn through a nozzle and pelletized to a required length.

[0055] Alternatively, an unmodified propylene polymer, an unsaturated carboxylic acid or anhydride thereof, and an organic peroxide may be dry-blended and then charged into the hopper of an extruder, whereby modification is simultaneously carried out while the mixture is being fed.

[0056] The method for impregnating the glass fiber roving with the molten resin is not particularly limited, and examples thereof include the method described in paragraph

[0036] of International Publication No. 2010 / 137305.

[0057] In the process of melting the resin, an extruder having two or more feed sections may be used, with a decomposing agent being fed through a top feed and another resin being fed through a side feed. Organic peroxides are preferred as the decomposing agent. Alternatively, two or more extruders (extrusion sections) may be used, with the decomposing agent being fed into at least one of them. Furthermore, the resin, unsaturated carboxylic acid or its derivative, and decomposing agent may be fed into at least one of the extruders.

[0058] (Propylene-based resin that may be added separately from glass fiber reinforced resin pellets) When the propylene-based resin (P1) contained in the glass fiber reinforced resin pellets is a part of the propylene-based resin, the glass fiber reinforced propylene-based resin composition of the present invention contains the remaining propylene-based resin (hereinafter also referred to as "propylene-based resin (P2)") in addition to the propylene-based resin (P1).

[0059] The propylene-based resin (P2) is a polymer containing propylene-derived structural units as the main structural units, and examples thereof include propylene homopolymers, propylene-α-olefin random copolymers, and propylene-based block copolymers.

[0060] The details of the propylene-α-olefin random copolymer and the propylene-based block copolymer are as described above.

[0061] 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 min, more preferably 20 to 250 g / 10 min, and even more preferably 20 to 200 g / 10 min. When 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.

[0062] Examples of the form of the propylene-based resin (P2) include powder and pellets.

[0063] Carbon Black The glass fiber reinforced propylene resin composition of the present invention contains carbon black.

[0064] The carbon black content in the composition of the present invention is 0.12 parts by mass or more, preferably 0.15 to 1.0 parts by mass, per 100 parts by mass of the glass fiber and the propylene-based resin combined. When the carbon black content is within this range, the generation of white haze is suppressed in reinforced fiber moldings produced from the glass fiber-reinforced propylene-based resin composition, even in large moldings. On the other hand, when the content is less than 0.12 parts by mass, the generation of white haze may not be suppressed. Furthermore, when 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.

[0065] Examples of carbon black include furnace black, acetylene black, thermal black, and channel black.

[0066] <Polyolefin wax> The glass fiber reinforced propylene resin composition of the present invention contains a polyolefin wax having an average particle size of 1 to 40 μm. This average particle size is determined by the D 50 is.

[0067] When the average particle size of the polyolefin wax is within this range, the polyolefin wax can be effectively arranged between carbon black particles to prevent aggregation of the carbon black particles, improving the dispersibility of the carbon black in the resin component and thereby suppressing the occurrence of white haze in the molded product. On the other hand, if the average particle size is much smaller than the lower limit, it may be difficult to produce the polyolefin wax, and if the average particle size is much larger than the upper limit, the dispersibility of the carbon black may decrease and the occurrence of white haze in the molded product may not be suppressed.

[0068] In the technology for suppressing the occurrence of white haze in molded articles made of glass fiber reinforced propylene-based resin compositions by blending an ethylene-based polymer, there is a tendency for the mechanical properties of the molded articles to decrease as the amount of ethylene-based polymer increases. However, according to the present invention, the occurrence of white haze is suppressed by blending carbon black and polyolefin wax, so it is expected that there will be no concerns when blending the above-mentioned ethylene-based polymer.

[0069] The polyolefin wax preferably has a polystyrene-equivalent number average molecular weight (Mn) of 2,000 to 10,000, more preferably 3,000 to 4,000, as measured by gel permeation chromatography (GPC) under the following conditions or equivalent conditions.

[0070] Apparatus: Gel permeation chromatograph Alliance GPC2000 (Waters) Solvent: o-dichlorobenzene Columns: TSKgel GMH6-HT x 2, TSKgel GMH6-HTL columns x 2 (both manufactured by Tosoh Corporation) Flow rate: 1.0ml / min Sample: 0.15 mg / mL o-dichlorobenzene solution Temperature: 140℃ The mass ratio of polyolefin wax to carbon black (mass of polyolefin wax / mass of carbon black) is 0.75 to 2.0, preferably 0.80 to 1.0. When the mass ratio is within this range, the polyolefin wax is effectively disposed between the carbon black particles, preventing aggregation of the carbon black particles and improving the dispersibility of the carbon black in the resin component, thereby suppressing the occurrence of whitish haze in the molded product. On the other hand, when the mass ratio is much lower than the lower limit, the dispersibility of the carbon black is low, and the occurrence of whitish haze in the molded product may not be suppressed.

[0071] As the polyolefin wax, polyethylene wax and polypropylene wax are preferred, and polypropylene wax is more preferred.

[0072] The polyolefin wax may be used alone or in combination of two or more kinds.

[0073] Zinc sulfide The glass fiber-reinforced propylene-based resin composition of the present invention contains zinc sulfide as a white pigment. Therefore, the molded article obtained from the glass fiber-reinforced propylene-based resin composition of the present invention can be easily adjusted in color tone and has excellent mechanical properties. On the other hand, when other white pigments, such as titanium oxide, are used, the mechanical properties of the molded article may be impaired.

[0074] The content of zinc sulfide in the composition of the present invention is more than 0 part by mass and not more than 1.3 parts by mass, preferably 0.1 to 1.0 part by mass, per 100 parts by mass of the total of the glass fiber and the propylene-based resin. If the content exceeds the upper limit, the remaining fiber length in the molded article may decrease, resulting in insufficient mechanical strength. Furthermore, if the remaining fiber length decreases, even if short-term mechanical strength is achieved, long-term properties such as creep characteristics and vibration fatigue may not be fully achieved. On the other hand, if the composition of the present invention does not contain zinc sulfide or other white pigments, molded articles obtained from the glass fiber-reinforced propylene-based resin composition containing carbon black will be excessively black.

[0075] Other ingredients The glass fiber reinforced propylene resin composition of the present invention may contain, as necessary, polymers other than the above-mentioned components, as long as the effects of the present invention are not impaired. Examples of such polymers include ethylene polymers, and examples of ethylene polymers include the ethylene polymers described in paragraphs

[0054] to

[0060] of WO 2020 / 091051.

[0076] In addition to the above components, the glass fiber reinforced propylene resin composition of the present invention may contain additives such as heat stabilizers, antistatic agents, weather stabilizers, light stabilizers, antioxidants, antioxidants, copper inhibitors, fatty acid metal salts, softeners, dispersants (excluding the polyolefin wax), fillers, colorants, pigments, and foaming agents, as needed, within the range that does not impair the effects of the present invention (for example, in a proportion of 5% by mass or less relative to 100% by mass of the composition). These components may be prepared as masterbatches.

[0077] (Glass fiber reinforced propylene resin composition) The glass fiber reinforced propylene resin composition of the present invention comprises: 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, and more preferably 60 to 80 parts by mass of the propylene-based resin (where the total of the glass fiber and the propylene-based resin is 100 parts by mass); the carbon black is 0.12 parts by mass or more, preferably 0.15 to 1.0 parts by mass; the polyolefin wax in an amount such that the mass ratio of the polyolefin wax to the carbon black is 0.75 to 2.0, preferably 0.80 to 1.0; and The coating composition contains zinc sulfide in an amount of more than 0 part by mass and not more than 1.3 parts by mass, preferably 0.1 to 1.0 part by mass.

[0078] When the content of each component is within the above range, a molded product in which the generation of white haze is suppressed can be produced.

[0079] (Method for producing glass fiber reinforced propylene resin composition) The glass fiber-reinforced propylene-based resin composition of the present invention can be produced by mixing, for example, dry blending, the glass fiber, the propylene-based resin, the carbon black, the polyolefin wax, the zinc sulfide, and optionally the additives.

[0080] A part or all of the propylene-based resin and the glass fibers are preferably mixed in the form of the above-mentioned glass fiber reinforced resin pellets.

[0081] Further, examples of the method for producing the glass fiber reinforced propylene resin composition of the present invention include the following: (1) a step of kneading a specified amount of pigment (carbon black, zinc sulfide) and pigment dispersant (polyolefin wax) into the propylene-based resin by melt kneading; and Step (2) of dry-blending the mixture obtained in step (1) with glass fiber reinforced resin pellets. A manufacturing method comprising: A step (1) of obtaining a color masterbatch by kneading a specified amount of pigment (carbon black, zinc sulfide) and pigment dispersant (polyolefin wax); A step (2) of dry-blending the glass fiber reinforced resin pellets, the propylene-based resin, and the color masterbatch obtained in the step (1). A manufacturing method including Examples include:

[0082] By carrying out step (2) by dry blending rather than melt kneading, breakage of the glass fibers can be prevented and a molded article having excellent mechanical properties can be produced.

[0083] [Glass fiber reinforced molding] The glass fiber reinforced molding according to the present invention comprises a composition containing the glass fiber, the propylene-based resin, the carbon black, the polyolefin wax, the zinc sulfide, and optionally the additive.

[0084] The details of each component are as described above unless otherwise specified. Furthermore, the content and technical significance of each component in the composition are the same as those of the glass fiber-reinforced propylene-based resin composition according to the present invention described above unless otherwise specified.

[0085] The length of the glass fibers in the molded product 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 fibers in the glass fiber-reinforced molded product of the present invention is usually 0.5 to 5 mm, preferably 0.8 to 3 mm, expressed as a weight-average fiber length calculated by extracting a predetermined number (1,000) of glass fibers from the molded product, measuring the length of each fiber, and calculating based on the following formula:

[0086] Weight average fiber length = Σ(fiber length) 2 / Σ fiber length The glass fiber-reinforced molding according to the present invention can be produced by molding a resin composition containing the glass fiber, the propylene-based resin, the carbon black, the polyolefin wax, the zinc sulfide, and optionally the additives, for example, the above-mentioned glass fiber-reinforced propylene-based resin composition according to the present invention.

[0087] As the molding method, known molding methods such as injection molding, extrusion molding, blow molding, compression molding, injection compression molding, gas injection molding or foam injection molding can be applied without any particular restrictions, and among these, injection molding, compression molding and injection compression molding are particularly preferred, and from the viewpoint of producing a molded product with excellent appearance (i.e., with suppressed generation of haze), injection molding is preferred.

[0088] The molded article of the present invention can be suitably used in various fields such as automobile interior and exterior parts, home appliance parts, etc. Examples of automobile interior and exterior parts include inner materials for back doors. [Example]

[0089] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0090] (Measurement method) The methods for measuring or evaluating various physical properties are as follows.

[0091] [Average particle size] The average particle size of the dispersant is determined by the D in the volume-based particle size distribution measured by the laser diffraction method. 50 was adopted.

[0092] [Remaining fiber length] The sample was thoroughly incinerated at 600°C, dispersed in water, and the fiber length was measured using an optical microscope. More than 500 glass fibers were measured, and the average length was calculated.

[0093] [Appearance of molded product] The appearance of the molded articles produced in the examples was evaluated according to the following criteria.

[0094] ○: White haze is almost invisible △: White haze is visible, but it is less visible than × ×: The white haze is clearly visible (Raw materials used) The raw materials used in the examples are as follows.

[0095] Long-fiber GF reinforced PP pellets [Manufacturing Example 1] Long fiber reinforced resin pellets were produced using the pellet production device shown in Figure 1.

[0096] In Fig. 1, 10 is a die, 20 is an extruder that supplies molten resin to the die 10, 30 is a roll for the fiber bundle F, 40 is a group of tension rolls that apply a certain tension to the fiber bundle F that is drawn into the die 10, 50 is a cooling means for cooling the molten resin-impregnated fiber bundle drawn out from the die 10, 60 is a drawing roll for the fiber bundle, and 70 is a pelletizer that cuts the drawn molten resin-impregnated fiber bundle. In this device, three independent fiber bundles F are simultaneously impregnated with molten resin.

[0097] The specific manufacturing conditions are as follows:

[0098] Die: Attached to the tip of a 50mm diameter extruder, with four rods arranged in a straight line in the impregnation section Fiber bundle: Glass roving consisting of 4,000 glass fibers with a fiber diameter of 17 μm, surface-treated with aminosilane (manufactured by Nippon Electric Glass Co., Ltd., product name: T-431N) Preheating temperature: 200℃ Resin: Propylene polymer PP1 and maleic anhydride modified polypropylene mPP1 mixed in a mass ratio of PP1:mPP1 = 48:2 Melting temperature: 280℃ Rods: Four rods, 6mm diameter x 3mm length Under the above conditions, the fiber bundle was fed into a die while adjusting the amount of fiber bundle with a group of tension rolls and impregnated, then pulled out from the die and cooled, and then pelletized to produce glass fiber reinforced resin pellets with a particle length of 6 mm, a reinforcing fiber length of 6 mm, and a reinforcing fiber content of 50 mass%.

[0099] The raw materials used are as follows:

[0100] PP1 (propylene homopolymer (MFR (230°C, 2.16 kg load) = 200 g / 10 min)) mPP1 (modified polypropylene, manufactured by Adivant, product name: POLYBOND3200 (MFR (230°C, 2.16 kg load) = 200 g / 10 min)) <Propylene-based resin> PP2 (propylene homopolymer, MFR (230°C, 2.16 kg load) = 30 g / 10 min) PP3 (propylene homopolymer, MFR (230°C, 2.16 kg load) = 60 g / 10 min) Carbon Black HIBLACK 890B (product name) (manufactured by Orion Engineered Carbons, average primary particle size = 15 nm) BLACK PEARLS 4840 (product name) (manufactured by Cabot, average primary particle size = 18 nm) <Dispersant> CERIDUST 6050M (product name) (fine particle polyolefin wax, average particle size = 12 μm, manufactured by Clariant) NP500 (product name) (polypropylene wax, manufactured by Mitsui Chemicals, average particle size = 267 μm) NL100 (product name) (polyethylene wax, manufactured by Mitsui Chemicals, average particle size = 279 μm) PM-11 (product name) (calcium stearate, manufactured by NOF Corp.) White pigment SACHTOLITH HD-S (trade name) (zinc sulfide, manufactured by VENATOR) Typaque CR-63 (titanium oxide, manufactured by Ishihara Sangyo Kaisha) "others" Vynamon Green 600734 (product name) (green pigment, manufactured by Heubach) Irgazin Yellow L 1030 (product name) (yellow pigment, manufactured by BASF) [Example 1] 40 parts by mass of PP2 (propylene-based resin) were melt-kneaded with 0.16 parts by mass of BP4840 (carbon black), 0.18 parts by mass of CERIDUST6050M (fine particle polyolefin wax), 0.52 parts by mass of HD-S (zinc sulfide), and 0.04 parts by mass of Irgazin Yellow L1030 (organic yellow) to obtain black pellets, which were dry-blended with 60 parts by mass of the glass fiber reinforced resin pellets obtained in Production Example 1 to prepare a glass fiber reinforced resin composition.

[0101] Next, a molded article was produced from this glass fiber reinforced resin composition using an injection molding machine under the following conditions, and the appearance of the molded article was evaluated.

[0102] Mold: 350mm x 150mm x 2mm, with a 60μm deep satin texture Molding temperature: 210℃ Mold temperature: 40℃ Gate: Side gate (center of short side) The evaluation results are shown in Table 1.

[0103] [Examples 2 to 8, Comparative Examples 1 to 10] Glass fiber reinforced resin compositions were prepared and molded articles were produced in the same manner as in Example 1, except that the raw materials and amounts of the compositions were changed as shown in Table 1 or Table 2.

[0104] The evaluation results are shown in Table 1 or Table 2.

[0105] [Table 1]

[0106] [Table 2] In the examples, the brightness of the molded body decreased by increasing the proportion of carbon black, and the brightness of the molded body increased by increasing the proportion of zinc sulfide, making it easy to adjust the color tone of the molded body.

[0107] In Comparative Examples 2 and 10, which did not contain zinc sulfide or other white pigments, the molded articles were excessively black. [Explanation of symbols]

[0108] 10 Die 20 Extruder 30 Roll of fiber bundle F 40 Tension Roll Group 50 Cooling means 60 drawer rolls 70 Pelletizer

Claims

1. 10 to 50 parts by mass of glass fiber, 50 to 90 parts by mass of propylene-based resin (wherein the total of the glass fiber and the propylene-based resin is 100 parts by mass), 0.12 parts by mass or more of carbon black, a polyolefin wax having an average particle size of 1 to 40 μm in an amount such that the mass ratio of the polyolefin wax to the carbon black is 0.75 to 2.0; and Contains more than 0 parts by mass and not more than 1.3 parts by mass of zinc sulfide, the propylene-based resin has a melt flow rate (in accordance with ISO 1133-1, 230°C, 2.16 kg load) of 25 to 500 g / 10 min; The polyolefin wax has a number average molecular weight (Mn) of 2,000 to 10,000 in terms of polystyrene as measured by gel permeation chromatography (GPC). Glass fiber reinforced propylene resin composition.

2. 2. The glass fiber reinforced propylene resin composition according to claim 1, wherein the content of the glass fiber is 25 to 50 parts by mass.

3. 3. The glass fiber reinforced propylene resin composition according to claim 1, wherein the polyolefin wax is a polypropylene wax.

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