JP2021195488A - Thermoplastic resin composition - Google Patents

Abstract

To provide a thermoplastic resin composition which contains a polyamide resin, a polyolefin resin, a compatibilizer and a filler, and is excellent in rigidity and ductility.SOLUTION: A thermoplastic resin composition contains a polyamide resin, a polyolefin resin, a compatibilizer and a filler. With respect to 100 mass% of the total of the polyamide resin, the polyolefin resin and the compatibilizer, a content of the polyamide resin is 35-75 mass%, a content of the polyolefin resin is 15-55 mass%, a content of the compatibilizer is 5-30 mass%, and a melt flow rate of the polyolefin resin measured on conditions of a temperature of 230°C and a load of 21.18 N is 23 g/10 min or more.SELECTED DRAWING: None

Description

The present invention relates to a thermoplastic resin composition, and more particularly to a thermoplastic resin composition containing a polyamide resin and a polyolefin resin.

Conventionally, for the purpose of improving the physical properties of resins, polymer blends and polymer alloys in which resins having different properties are mixed to modify the properties of the resins have been actively studied. For example, International Publication No. 2018/135648 (Patent Document 1) comprises a polyolefin resin, a polyamide resin containing an inorganic filler, and a modified elastomer having a reactive group for the polyamide resin. The resin has a number average molecular weight of 350,000 or more, and the polyamide resin has a structure in which the linear carbon number of the hydrocarbon group sandwiched between adjacent amide bonds in the main chain is 5 or less. , A thermoplastic resin composition having both impact resistance and rigidity is disclosed. Further, Japanese Patent Application Laid-Open No. 2014-25060 (Patent Document 2) contains a polyamide resin, a polyolefin resin, and a modified elastomer having a reactive group capable of reacting with the polyamide resin, and is composed of a specific resin phase. A resin composition having a dispersed structure, excellent impact resistance, and excellent rigidity is disclosed.

International Publication No. 2018/135648 Japanese Unexamined Patent Publication No. 2014-25060

However, in order to use a conventional thermoplastic resin composition containing a polyamide resin, a polyolefin resin, a compatibilizer, and a filler as a substitute material for a metal material in automobile parts and the like, it is not always sufficient to achieve both rigidity and ductility. There wasn't.

The present invention has been made in view of the above-mentioned problems of the prior art, and is a thermoplastic resin composition containing a polyamide resin, a polyolefin resin, a compatibilizer and a filler, and having both high rigidity and ductility. The purpose is to provide.

As a result of diligent research to achieve the above object, the present inventors have made a specific melt flow as the polyolefin resin in a thermoplastic resin composition containing a polyamide resin, a polyolefin resin, a compatibilizer and a filler. By using a material having a rate, it has been found that the ductility is improved and both high rigidity and ductility are compatible, and the present invention has been completed.

That is, the thermoplastic resin composition of the present invention contains a polyamide resin, a polyolefin resin, a compatibilizer, and a filler.
The content of the polyamide resin is 35 to 75% by mass and the content of the polyolefin resin is 15 to 55% by mass with respect to a total of 100% by mass of the polyamide resin, the polyolefin resin and the compatibility agent. The content of the compatibilizer is 5 to 30% by mass, and the melt flow rate of the polyolefin resin measured under the conditions of a temperature of 230 ° C. and a load of 21.18 N is 23 g / 10 min or more. It is characterized by.

In the thermoplastic resin composition of the present invention, the compatibility agent is preferably a modified elastomer having a reactive group capable of reacting with the polyamide resin, and is a maleic anhydride-modified ethylene-1-butene copolymer. It is more preferable that the polyolefin resin is polypropylene.

Further, in the thermoplastic resin composition of the present invention, the filler is preferably carbon fiber having an average length of 6 mm or less, and the polyamide resin is composed of a group consisting of polyamide 6, polyamide 66 and polyamide 11. It is preferably at least one selected.

Although the reason why the ductility is improved in the thermoplastic resin composition of the present invention is not always clear, the present inventors infer as follows. That is, the thermoplastic resin composition of the present invention is compatible with a polyamide resin and a polyolefin resin having a melt flow rate (MFR) of 23 g / 10 min or more measured under the conditions of a temperature of 230 ° C. and a load of 21.18 N. It contains an agent and a filler. In such a thermoplastic resin composition, since the polyolefin resin having an MFR within the above range acts as a plasticizer, it is presumed that the ductility is improved.

According to the present invention, it is possible to obtain a thermoplastic resin composition containing a polyamide resin, a polyolefin resin, a compatibilizer and a filler, and having both high rigidity and ductility.

Hereinafter, the present invention will be described in detail according to the preferred embodiment thereof.

The thermoplastic resin composition of the present invention contains a polyamide resin, a polyolefin resin, a compatibilizer, and a filler.

(Polyamide resin)
The polyamide resin used in the present invention is a polymer having a chain-like skeleton in which a plurality of monomers are polymerized via an amide bond (-NH-CO-). Examples of the monomer include amino acids, lactams, diamines and dicarboxylic acids. Examples of the amino acid include 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, paraaminomethylbenzoic acid and the like, and examples of the lactam include ε-caprolactam, undecanlactam, ω-lauryl lactam and the like. Be done. The diamines include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, and 1,8-diaminooctane. , 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, 1,14-diaminotetradecane, 1,15-diaminopentadecan , 1,16-Diaminohexadecane, 1,17-diaminoheptadecan, 1,18-diaminooctadecane, 1,19-diaminononadecan, 1,20-diaminoeikosan, 2-methyl-1,5-diaminopentane, Aliphatic diamines such as 2-methyl-1,8-diaminooctane; alicyclic diamines such as cyclohexanediamine and bis- (4-aminocyclohexyl) methane; xylylene diamines, p-phenylenediamines, m-phenylenediamines and the like. Examples include aromatic diamines. Further, examples of the dicarboxylic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelli acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, brushphosphoric acid, and tetradecanedioic acid. Examples thereof include aliphatic dicarboxylic acids such as pentadecanedioic acid and octadecanedioic acid; alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid; aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid. These monomers may be used alone or in combination of two or more.

The polyamide resin used in the present invention is not particularly limited, but specifically, polyamide 11 (PA11), polyamide 6 (PA6), polyamide 66 (PA66), polyamide 610 (PA610), polyamide 612 (PA612), and the like. Polyamide 12 (PA12), Polyamide 6T (PA6T), Polyamide 6I, Polyamide 9T, Polyamide M5T, Polyamide 1010 (PA1010), Polyamide 1012 (PA1012), Polyamide 10T, Polyamide MXD6, Polyamide 6T / 66, Polyamide 6T / 6I, Polyamide Examples thereof include 6T / 6I / 66, polyamide 6T / 2M-5T, and polyamide 9T / 2M-8T. These polyamide resins may be used alone or in combination of two or more. Further, among these polyamide resins, PA6, PA66, and PA11 are preferable, and PA6 is more preferable, from the viewpoint of improving the impact resistance of the thermoplastic resin composition.

The number average molecular weight (Mn) of the polyamide resin is not particularly limited, but is preferably 5,000 to 100,000, more preferably 5,000 to 70,000, still more preferably 10,000 to 40,000. The weight average molecular weight (Mw) of the polyamide resin is not particularly limited, but is preferably 5,000 to 100,000, more preferably 7,500 to 80,000, and further preferably 10,000 to 70,000. preferable. The number average molecular weight and the weight average molecular weight are measured by gel permeation chromatography (GPC) and converted into standard polystyrene.

(Polyolefin resin)
The polyolefin resin used in the present invention has a melt flow rate (MFR) of 23 g / 10 min or more measured in accordance with JIS K7210 under the conditions of a temperature of 230 ° C. and a load of 21.18 N. By using such a polyolefin resin having MFR, it is possible to obtain a thermoplastic resin composition having both high rigidity and ductility. On the other hand, if the MFR is less than the lower limit, the ductility of the thermoplastic resin composition is not improved. Further, from the viewpoint of improving the ductility of the thermoplastic resin composition, the MFR is preferably 30 g / 10 min or more, more preferably 40 g / 10 min or more, still more preferably 50 g / 10 min or more.

The polyolefin resin is not particularly limited, but is an ethylene homopolymer (polyethylene), a propylene homopolymer (polypropylene), an ethylene-propylene copolymer, an ethylene-α-olefin copolymer, and a propylene-α-olefin copolymer. Coalescence and the like can be mentioned. Examples of the α-olefin include unsaturateds having 3 to 20 carbon atoms such as 1-butene, 1-pentene, 1-hexene, 1-hexene, 3-methyl-1-butene and 4-methyl-1-pentene. Hydrocarbons can be mentioned. These polyolefin resins may be used alone or in combination of two or more. Further, among these polyolefin resins, from the viewpoint of further improving the rigidity of the thermoplastic resin composition, a propylene-based resin having a constituent unit derived from propylene as a main constituent unit and a constituent unit derived from ethylene as the main constituent unit are used. The ethylene-based resin having the above is preferable, and the propylene-based resin is more preferable. Further, as such a propylene-based resin and an ethylene-based resin, the content of the structural unit derived from propylene or ethylene is the propylene-based resin or ethylene, respectively, from the viewpoint of further improving the rigidity of the thermoplastic resin composition. Of all the constituent units in the based resin, those having 50 mol% or more are preferable, and those having 100 mol% (polypropylene or polyethylene) are more preferable.

The number average molecular weight (Mn) of the polyolefin resin is not particularly limited, but is preferably 5,000 to 500,000, more preferably 10,000 to 450,000, still more preferably 10,000 to 400,000. The weight average molecular weight (Mw) of the polyolefin resin is not particularly limited, but is preferably 10,000 to 500,000, more preferably 50,000 to 450,000, and further preferably 100,000 to 400,000. preferable. The number average molecular weight and the weight average molecular weight are measured by gel permeation chromatography (GPC) and converted into standard polystyrene.

The polyolefin resin used in the present invention is different from the modified elastomer described later in that it is incompatible with the polyamide resin and has substantially no reactive group capable of binding to the polyamide resin. It is a thing.

(Compatible agent)
Examples of the compatibilizer used in the present invention include modified elastomers having a reactive group capable of reacting with the polyamide resin. By using such a modified elastomer as a compatibility agent, a thermoplastic resin composition having both high rigidity and ductility and excellent impact resistance can be obtained. On the other hand, when a polyolefin resin having a reactive group capable of reacting with the polyamide resin (excluding the modified elastomer) is used instead of the modified elastomer having a reactive group capable of reacting with the polyamide resin, the thermoplastic resin is used. The impact resistance and elongation of the composition are reduced.

Examples of the modified elastomer include the modified olefin-based thermoplastic elastomer having the reactive group and the modified styrene-based thermoplastic elastomer having the reactive group.

Examples of the olefin-based thermoplastic elastomer constituting the modified olefin-based thermoplastic elastomer having a reactive group include 2 of α-olefins such as ethylene, propylene, 1-butene, 1-pentene, and 1-octene. Examples thereof include copolymers of monomers of more than one species. These copolymers may be used alone or in combination of two or more. Further, among these copolymers, from the viewpoint of further improving the rigidity and impact resistance of the thermoplastic resin composition, a copolymer of ethylene and an α-olefin having 3 to 8 carbon atoms, and propylene. A copolymer with an α-olefin having 4 to 8 carbon atoms is preferable. Specific examples of such an olefin-based thermoplastic elastomer include an ethylene-propylene copolymer (EPR), an ethylene-1-butene copolymer (EBR), an ethylene-1-pentene copolymer, and an ethylene-1-. Examples thereof include an octene copolymer (EOR), a propylene-1-butene copolymer (PBR), a propylene-1-pentene copolymer, and a propylene-1-octene copolymer (POR).

Examples of the styrene-based thermoplastic elastomer constituting the modified styrene-based thermoplastic elastomer having a reactive group include a block copolymer of a styrene-based compound and a conjugated diene compound or the α-olefin, and a hydrogenated product thereof. Can be mentioned. These copolymers may be used alone or in combination of two or more. Examples of the styrene-based compound include styrene; alkyl styrene such as α-methyl styrene, p-methyl styrene, and pt-butyl styrene; p-methoxy styrene; vinyl naphthalene. Examples of the conjugated diene compound include butadiene, isoprene, piperylene, methylpentadiene, phenylbutadiene, 3,4-dimethyl-1,3-hexadiene, and 4,5-diethyl-1,3-octadien. Specific examples of such styrene-based thermoplastic elastomers include styrene-butadiene-styrene copolymer (SBS), styrene-isoprene-styrene copolymer (SIS), and styrene-ethylene / butylene-styrene copolymer (Styrene-ethylene / butylene-styrene copolymer). SEBS), styrene-ethylene / propylene-styrene copolymer (SEPS).

Examples of the reactive group that can be bonded to the polyamide resin include a functional group that can be covalently bonded to the polyamide resin, specifically, an acid anhydride group (-CO-O-OC-), a carboxyl group (-COOH), and the like. Examples thereof include an epoxy group [-C ₂ O (three-membered ring structure consisting of two carbon atoms and one oxygen atom)], an oxazoline group (-C ₃ H ₄ NO), and an isocyanate group (-NCO). Of these functional groups, an acid anhydride group is preferable from the viewpoint of high reactivity. The proportion of the reactive group in the modified elastomer is preferably 0.5% by mass or more, more preferably 0.5 to 5% by mass.

Further, the method for imparting the reactive group to the olefin-based thermoplastic elastomer and the styrene-based thermoplastic elastomer is not particularly limited, and a known method can be appropriately used. For example, as a method of imparting the acid anhydride group to the elastomer, a method of further adding acid anhydride as a monomer of the elastomer can be mentioned. Examples of the acid anhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, succinic anhydride, glutaric anhydride, adipic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, and succinic anhydride. These acid anhydrides may be used alone or in combination of two or more. Among these acid anhydrides, maleic anhydride, phthalic anhydride, and itaconic anhydride are preferable, and maleic anhydride is more preferable, from the viewpoint of high reactivity.

Examples of the modified elastomer having the reactive group used in the present invention include maleic anhydride-modified EPR, maleic anhydride-modified PBR, maleic anhydride-modified EBR, maleic anhydride-modified EOR, and maleic anhydride-modified POR. Modified olefin-based thermoplastic elastomers; examples thereof include maleic anhydride-modified styrene-based thermoplastic elastomers such as maleic anhydride-modified SEBS, maleic anhydride-modified SBS, maleic anhydride-modified SIS, and maleic anhydride-modified SEPS. These modified elastomers may be used alone or in combination of two or more. Further, among these modified elastomers, the modified olefin-based thermoplastic elastomer having the reactive group is preferable, has high reactivity, is more compatible with the polyolefin resin, and has rigidity and resistance of the thermoplastic resin composition. From the viewpoint of further improving the impact resistance, maleic anhydride-modified PBR, maleic anhydride-modified EBR, and maleic anhydride-modified EOR are more preferable.

The weight average molecular weight (Mw) of the modified elastomer having a reactive group is not particularly limited, but from the viewpoint that the larger the weight average molecular weight, the higher the impact resistance of the thermoplastic resin composition is, 10,000 to 10,000 to 500,000 is preferable, 20,000 to 500,000 is more preferable, and 25,000 to 400,000 is even more preferable. The weight average molecular weight is a value measured by gel permeation chromatography (GPC) and converted into standard polystyrene.

(Filler)
The filler used in the present invention is not particularly limited, and is inorganic fiber (glass fiber, alumina fiber, carbon fiber (carbon fiber), potassium titanate fiber, etc.); organic fiber (aromatic polyester fiber, aromatic polyamide fiber, fluorine). Resin fiber, polyimide fiber, vegetable fiber, etc.); glass, silica, graphite, silicate compound (calcium silicate, aluminum silicate, kaolin, talc, clay, etc.), metal oxide (iron oxide, titanium oxide, zinc oxide, antimony oxide, etc.) , Alumina, etc.), metal carbonates or sulfates (carbonates or sulfates such as calcium, magnesium, zinc) and the like, and examples thereof include particles and flakes. By blending such a filler, a thermoplastic resin composition having excellent rigidity can be obtained. These fillers may be used alone or in combination of two or more. Among these fillers, carbon fiber and glass fiber are preferable.

Further, the filler has an average length of preferably 6 mm or less, more preferably 3 mm or less, from the viewpoint of improving the fluidity and moldability of the thermoplastic resin composition. The average length can be obtained by measuring the length in the major axis direction (length of the longest axis) of 100 or more randomly selected fillers with an electron microscope and averaging the values.

Further, the filler preferably has an average aspect ratio of 10 or more, and more preferably 20 or more, from the viewpoint of increasing the effect of improving the rigidity of the thermoplastic resin composition. The average aspect ratio is the length in the major axis direction (length of the longest axis) and the diameter in the minor axis direction (maximum length of the surface orthogonal to the longest axis) of 100 or more randomly selected fillers. Is measured with an electronic microscope, the aspect ratio of each filler (the ratio of the length in the major axis direction to the diameter in the minor axis direction (length in the major axis direction / diameter in the minor axis direction)) is obtained, and the values are averaged. It can be obtained by.

[Thermoplastic resin composition]
The thermoplastic resin composition of the present invention contains the polyamide resin, the polyolefin resin, the compatibility agent, and the filler.

In the thermoplastic resin composition of the present invention, the content of the polyamide resin is 35 to 75% by mass with respect to 100% by mass of the total of the polyamide resin, the polyolefin resin and the compatibility agent. When the content of the polyamide resin is less than the lower limit, the impact resistance of the thermoplastic resin composition is lowered, while when the content exceeds the upper limit, the content of the polyolefin resin is relatively reduced, so that the thermoplasticity is high. The ductility of the resin composition is reduced. Further, from the viewpoint of further improving the impact resistance and ductility of the thermoplastic resin composition, the content of the polyamide resin is preferably 40 to 65% by mass.

Further, in the thermoplastic resin composition of the present invention, the content of the polyolefin resin is 15 to 55% by mass with respect to 100% by mass of the total of the polyamide resin, the polyolefin resin and the compatibility agent. When the content of the polyolefin resin is less than the lower limit, the ductility of the thermoplastic resin composition is lowered, while when the content exceeds the upper limit, the content of the polyamide resin is relatively reduced, and the thermoplastic resin composition is prepared. Impact resistance is reduced. Further, from the viewpoint of further improving the impact resistance and ductility of the thermoplastic resin composition, the content of the polyolefin resin is preferably 20 to 50% by mass.

Further, in the thermoplastic resin composition of the present invention, the content of the compatibility agent is 5 to 30% by mass with respect to 100% by mass of the total of the polyamide resin, the polyolefin resin and the compatibility agent. be. When the content of the compatibilizer is less than the lower limit, the impact resistance and ductility of the thermoplastic resin composition are lowered, while when the content exceeds the upper limit, the rigidity of the thermoplastic resin composition is lowered. Further, from the viewpoint of further improving the impact resistance, rigidity and ductility of the thermoplastic resin composition, the content of the compatibility agent is preferably 10 to 25% by mass.

Further, in the thermoplastic resin composition of the present invention, the content of the filler is preferably 50% by mass or less, more preferably 3 to 35% by mass, based on the entire thermoplastic resin composition. When the content of the filler is less than the lower limit, the rigidity of the thermoplastic resin composition tends to decrease, while when the content exceeds the upper limit, the moldability of the thermoplastic resin composition tends to decrease.

The thermoplastic resin composition of the present invention may contain a reaction product of the polyamide resin and the modified elastomer having a reactive group from the viewpoint of improving the impact resistance of the thermoplastic resin composition. preferable. Such a reactant is a component produced by the reaction of the reactive group of the modified elastomer with the polyamide resin. The method for obtaining such a reactant is not particularly limited. For example, when the thermoplastic resin composition of the present invention is produced, a mixed material containing the polyamide resin and the modified elastomer having a reactive group is heated. By melt-kneading, it can be produced in the thermoplastic resin composition of the present invention. The content of such a reactant is preferably 60% by mass or less, more preferably 5 to 50% by mass, based on the entire thermoplastic resin composition. When the content of the reactant exceeds the upper limit, the rigidity of the thermoplastic resin composition tends to decrease.

Further, in the thermoplastic resin composition of the present invention, for example, other thermoplastic resins other than the above, antioxidants, anti-ultraviolet agents, and thermal stability, as required, within a range that does not impair the effects of the present invention. Various additives such as an agent, a flame retardant, a flame retardant aid, a colorant, an antibacterial agent, an antistatic agent, a lubricant, a mold release agent, and a foaming agent may be contained. Such an additive may contain one kind alone or two or more kinds. The content of such additives is preferably 10% by mass or less in total with respect to the entire thermoplastic resin composition.

Examples of the other thermoplastic resin include polyester resins (polybutylene terephthalate, polyethylene terephthalate, polytrimethylene terephthalate, polybutylene succinate, polyethylene succinate, polylactic acid, polyhydroxyalkanoic acid), polycarbonate resins and the like. These thermoplastic resins may be used alone or in combination of two or more. Examples of the flame retardant include a halogen-based flame retardant (halogenated aromatic compound, etc.), a phosphorus-based flame retardant (nitrogen-containing phosphate compound, phosphoric acid ester, etc.), a nitrogen-based flame retardant (guanidine, triazine, melamine, and the like). , Inorganic flame retardants (metal hydroxides, etc.), boron flame retardants, silicone flame retardants, sulfur flame retardants, red phosphorus flame retardants, etc. These flame retardants may be used alone or in combination of two or more. Examples of the flame retardant aid include various antimony compounds, metal compounds containing zinc, metal compounds containing bismuth, magnesium hydroxide, viscous silicate and the like. These flame retardant aids may be used alone or in combination of two or more. Examples of the colorant include pigments and dyes. These colorants may be used alone or in combination of two or more.

(Manufacturing method of thermoplastic resin composition)
The thermoplastic resin composition of the present invention is obtained by mixing the polyamide resin, the polyolefin resin, the compatibility agent, the filler, and if necessary, other components so as to have a predetermined content. be able to. At this time, each component may be mixed all at once, or one kind or two or more kinds may be added and added (multi-stage blending) in a plurality of times and mixed. Examples of the mixing method include a kneading method using a kneading device. Examples of the kneading device include an extruder (single-screw extruder, twin-screw melt-kneading extruder, etc.), a kneader, and a mixer (high-speed flow mixer, paddle mixer, ribbon mixer, etc.). These kneading devices may be used alone or in combination of two or more. When two or more kinds of kneading devices are used in combination, they may be operated continuously or batchwise (in a batch system).

The kneading temperature is not particularly limited and is appropriately adjusted depending on the type of resin to be kneaded. Therefore, although it cannot be said unconditionally, each resin used in the present invention can be mixed in a molten state. From this point of view, 100 to 350 ° C. is preferable, 180 to 320 ° C. is more preferable, and 200 to 300 ° C. is further preferable.

[Molded product]
The thermoplastic resin composition of the present invention may be molded in any way, and the method thereof is not particularly limited. Further, the shape, size, thickness and the like of the obtained molded product are not particularly limited, and the use thereof is not particularly limited. For example, the molded body can be used as an exterior material, an interior material, a structural material, or the like for automobiles, railroad vehicles, ships, airplanes, and the like. The materials for automobiles include automobile exterior materials, automobile interior materials, automobile structural materials, automobile impact energy absorbers, automobile pedestrian protective materials, automobile occupant protective materials, engine room interior parts, and the like. Can be mentioned. Specifically, shock absorbing parts, bumpers, spoilers, cowlings, front grills, garnishes, bonnets, trunk lids, fender panels, door panels, roof panels, instrument panels, door trims, quarter trims, roof linings, pillar garnishes, decks. Trims, tonoboards, package trays, dashboards, console boxes, kicking plates, switch bases, seat backboards, seat frames, armrests, sun visors, intake manifolds, engine head covers, engine undercovers, oil filter housings, air filter boxes, automotive Examples include housings for electronic parts (ECU, TV monitor, etc.).

Further, the molded body may be, for example, an interior material such as a building or furniture, an exterior material and a structural material, specifically, a door covering material, a door structural material, various furniture (desk, chair, shelf, bag, etc.). It can also be used as a surface material, structural material, etc., as well as packaging, housing (tray, etc.), protective members, partition members, home appliances (thin TV, refrigerator, washing machine, vacuum cleaner, mobile phone, portable game). It can also be used as a housing and structure for machines, notebook computers, etc.) and bags (suitcases, etc.).

Hereinafter, the present invention will be described in more detail based on Examples and Comparative Examples, but the present invention is not limited to the following Examples.

(Example 1)
Polyamide 6 as a polyamide resin (PA6, "Amylan CM1007" manufactured by Toray Co., Ltd., number average molecular weight: 30,000, weight average molecular weight: 56,000) 40 parts by mass, maleic anhydride-modified ethylene-1- as a compatibilizer 10 parts by mass of butene copolymer (modified EBR-1, "Toughmer MH7020" manufactured by Mitsui Chemicals, Inc.), polypropylene as polyolefin resin (PP-1, "Novatec SA06GA" manufactured by Nippon Polypro Co., Ltd., MFR (temperature 230 ° C., load) 21.18N measured according to JIS K7210): 60g / 10min) 20 parts by mass, carbon fiber as filler (CF, "chopped CFTR06NE B4J" manufactured by Mitsubishi Chemical Corporation, average length: 6mm, average aspect ratio: 1000) Using a twin-screw melt-kneading extruder (“HK-25D” manufactured by Parker Corporation, screw diameter: 25 mm, L / D = 41), 30 parts by mass was used at a temperature of 230 ° C. and an extrusion speed of 10 kg / h. A thermoplastic resin composition was obtained by melt-kneading under the condition of a screw rotation speed of 400 rpm. This thermoplastic resin composition is injection-molded using an injection molding machine (“FNX140” manufactured by Nissei Plastic Industry Co., Ltd.) under the conditions of a set temperature of 230 ° C and a mold temperature of 40 ° C, and a dumbbell compliant with JIS K7139. A shape tensile test piece (multipurpose test piece) type A1 was produced.

(Example 2)
Conducted except using 20 parts by mass of polypropylene (PP-2, "YS559" manufactured by Sun Aroma Co., Ltd., MFR (measured according to JIS K7210 at a temperature of 230 ° C. and a load of 21.18 N): 60 g / 10 min) as the polyolefin resin. A thermoplastic resin composition was prepared in the same manner as in Example 1, and a dumbbell-shaped tensile test piece (multipurpose test piece) type A1 was further prepared using this thermoplastic resin composition.

(Example 3)
Except for using 20 parts by mass of polypropylene (PP-3, "Novatec HT40T" manufactured by Nippon Polypro Co., Ltd., MFR (measured according to JIS K7210 at a temperature of 230 ° C. and a load of 21.18 N): 24 g / 10 min) as the polyolefin resin. Prepared a thermoplastic resin composition in the same manner as in Example 1, and further prepared a dumbbell-shaped tensile test piece (multipurpose test piece) type A1 using this thermoplastic resin composition.

(Example 4)
Heat was applied in the same manner as in Example 1 except that 10 parts by mass of a maleic anhydride-modified ethylene-1-butene copolymer (modified EBR-2, “Toughmer MH5040” manufactured by Mitsui Chemicals Co., Ltd.) was used as a compatibilizer. A plastic resin composition was prepared, and further, a dumbbell-shaped tensile test piece (multipurpose test piece) type A1 was prepared using this thermoplastic resin composition.

(Example 5)
Except for using 20 parts by mass of polypropylene (PP-3, "Novatec HT40T" manufactured by Nippon Polypro Co., Ltd., MFR (measured according to JIS K7210 at a temperature of 230 ° C. and a load of 21.18 N): 24 g / 10 min) as the polyolefin resin. Prepared a thermoplastic resin composition in the same manner as in Example 4, and further prepared a dumbbell-shaped tensile test piece (multipurpose test piece) type A1 using this thermoplastic resin composition.

(Example 6)
A thermoplastic resin composition was prepared in the same manner as in Example 3 except that the amount of the polyamide resin was changed to 35 parts by mass and the amount of the polyolefin resin was changed to 25 parts by mass, and further, this thermoplastic resin composition was used. A dumbbell-shaped tensile test piece (multipurpose test piece) type A1 was produced.

(Example 7)
A thermoplastic resin composition was prepared in the same manner as in Example 4 except that the amount of the polyamide resin was changed to 35 parts by mass and the amount of the polyolefin resin was changed to 25 parts by mass, and further, this thermoplastic resin composition was used. A dumbbell-shaped tensile test piece (multipurpose test piece) type A1 was produced.

(Comparative Example 1)
Except for using 20 parts by mass of polypropylene (PP-4, "Novatec MA1B" manufactured by Nippon Polypro Co., Ltd., MFR (measured according to JIS K7210 at a temperature of 230 ° C. and a load of 21.18 N): 20 g / 10 min) as the polyolefin resin. Prepared a thermoplastic resin composition in the same manner as in Example 1, and further prepared a dumbbell-shaped tensile test piece (multipurpose test piece) type A1 using this thermoplastic resin composition.

(Comparative Example 2)
Except for using 20 parts by mass of polypropylene (PP-5, "Novatec MA3H" manufactured by Nippon Polypro Co., Ltd., MFR (measured according to JIS K7210 at a temperature of 230 ° C. and a load of 21.18 N): 10 g / 10 min) as the polyolefin resin. Prepared a thermoplastic resin composition in the same manner as in Example 1, and further prepared a dumbbell-shaped tensile test piece (multipurpose test piece) type A1 using this thermoplastic resin composition.

(Comparative Example 3)
Except for using 20 parts by mass of polypropylene (PP-6, "Novatec F113G" manufactured by Nippon Polypro Co., Ltd., MFR (measured according to JIS K7210 at a temperature of 230 ° C. and a load of 21.18 N): 3 g / 10 min) as the polyolefin resin. Prepared a thermoplastic resin composition in the same manner as in Example 1, and further prepared a dumbbell-shaped tensile test piece (multipurpose test piece) type A1 using this thermoplastic resin composition.

(Comparative Example 4)
Except for using 20 parts by mass of polypropylene (PP-6, "Novatec F113G" manufactured by Nippon Polypro Co., Ltd., MFR (measured according to JIS K7210 at a temperature of 230 ° C. and a load of 21.18 N): 3 g / 10 min) as the polyolefin resin. Prepared a thermoplastic resin composition in the same manner as in Example 4, and further prepared a dumbbell-shaped tensile test piece (multipurpose test piece) type A1 using this thermoplastic resin composition.

(Comparative Example 5)
Performed except that 10 parts by mass of maleic anhydride-modified polypropylene (modified PP, "UMEX1010" manufactured by Sanyo Kasei Kogyo Co., Ltd.) was used instead of the maleic anhydride-modified ethylene-1-butene copolymer (modified EBR-1). A thermoplastic resin composition was prepared in the same manner as in Example 1, and a dumbbell-shaped tensile test piece (multipurpose test piece) type A1 was further prepared using this thermoplastic resin composition.

(Comparative Example 6)
A thermoplastic resin composition was prepared in the same manner as in Comparative Example 1 except that the amount of the polyamide resin was changed to 35 parts by mass and the amount of the polyolefin resin was changed to 25 parts by mass, and further, this thermoplastic resin composition was used. A dumbbell-shaped tensile test piece (multipurpose test piece) type A1 was produced.

(Comparative Example 7)
A thermoplastic resin composition was prepared in the same manner as in Comparative Example 2 except that the amount of the polyamide resin was changed to 35 parts by mass and the amount of the polyolefin resin was changed to 25 parts by mass, and further, this thermoplastic resin composition was used. A dumbbell-shaped tensile test piece (multipurpose test piece) type A1 was produced.

(Comparative Example 8)
A thermoplastic resin composition was prepared in the same manner as in Comparative Example 3 except that the amount of the polyamide resin was changed to 35 parts by mass and the amount of the polyolefin resin was changed to 25 parts by mass, and further, this thermoplastic resin composition was used. A dumbbell-shaped tensile test piece (multipurpose test piece) type A1 was produced.

(Comparative Example 9)
A thermoplastic resin composition was prepared in the same manner as in Comparative Example 4 except that the amount of the polyamide resin was changed to 35 parts by mass and the amount of the polyolefin resin was changed to 25 parts by mass, and further, this thermoplastic resin composition was used. A dumbbell-shaped tensile test piece (multipurpose test piece) type A1 was produced.

<Measurement of flexural modulus>
For each test piece obtained in Examples and Comparative Examples, the distance between fulcrums is 64 mm, the test speed (relative movement between the indenter (tip radius 5 mm) arranged in the center between fulcrums and the support base) in accordance with JIS K7171. The flexural modulus was measured under the condition of speed) 2 mm / min. The results are shown in Tables 1 and 2.

<Measurement of elongation at break>
Each test piece obtained in Examples and Comparative Examples was measured for breaking elongation under the conditions of a distance between gripping tools of 115 mm and a test speed (tensile speed) of 5 mm / min in accordance with JIS K7161, and evaluated according to the following criteria. .. The results are shown in Tables 1 and 2.
A: Break elongation is 4% or more.
B: Breaking elongation is less than 4%.

<Comprehensive evaluation>
It was evaluated according to the following criteria based on the flexural modulus and elongation at break. The results are shown in Tables 1 and 2.
A: The flexural modulus is 8 GPa or more and the breaking elongation is 4% or more.
B: The flexural modulus is less than 8 GPa or the elongation at break is less than 4%.

As shown in Tables 1 and 2, in a thermoplastic resin composition containing a polyamide resin, a polyolefin resin, a compatibilizer, and a filler, MFR (temperature 230 ° C., load 21.18N) is used as the elastomer resin. When a polyolefin resin of 23 g / 10 min or more is used and a maleic anhydride-modified elastomer is used as the compatibility agent (Examples 1 to 7), the MFR (temperature 230 ° C., load 21.18 N) is used as the polyolefin resin. When a polyolefin resin having a weight of 20 g / 10 min or less is used (Comparative Examples 1 to 4 and Comparative Examples 6 to 9) and when anhydrous maleic acid-modified polypropylene is used instead of the anhydrous maleic acid-modified elastomer (Comparative Example 5). In comparison, it was found that the elongation at break was increased, the elongation was improved, and both high rigidity and elongation were compatible.

As described above, according to the present invention, it is possible to obtain a thermoplastic resin composition containing a polyamide resin, a polyolefin resin, a compatibilizer, and a filler, and having both high rigidity and ductility. Therefore, since the thermoplastic resin composition of the present invention has both high rigidity and ductility, it is useful as an exterior material, interior material, structural material, etc. for automobiles, railroad vehicles, ships, airplanes, buildings, furniture, and the like. Is.

Claims (6)

Contains polyamide resin, polyolefin resin, compatibility agent and filler,
With respect to a total of 100% by mass of the polyamide resin, the polyolefin resin, and the compatibility agent.
The content of the polyamide resin is 35 to 75% by mass, and the content is 35 to 75% by mass.
The content of the polyolefin resin is 15 to 55% by mass, and the content is 15 to 55% by mass.
The content of the compatibility agent is 5 to 30% by mass, and the content thereof is 5 to 30% by mass.
The melt flow rate of the polyolefin resin measured under the conditions of a temperature of 230 ° C. and a load of 21.18 N is 23 g / 10 min or more.
A thermoplastic resin composition characterized by this. The thermoplastic resin composition according to claim 1, wherein the compatible agent is a modified elastomer having a reactive group capable of reacting with the polyamide resin. The thermoplastic resin composition according to claim 2, wherein the compatibilizer is a maleic anhydride-modified ethylene-1-butene copolymer. The thermoplastic resin composition according to any one of claims 1 to 3, wherein the polyolefin resin is polypropylene. The thermoplastic resin composition according to any one of claims 1 to 4, wherein the filler is a carbon fiber having an average length of 6 mm or less. The thermoplastic resin composition according to any one of claims 1 to 5, wherein the polyamide resin is at least one selected from the group consisting of polyamide 6, polyamide 66 and polyamide 11.