Resin composition and molding

Abstract

To provide a resin composition from which a molding excellent in impact strength and rigidity can be obtained.SOLUTION: A resin composition contains a polyamide resin, a glass filler, and a copolymer of a carboxylic acid and / or a carboxylic acid derivative and α-olefin, wherein a structural unit derived from the carboxylic acid and / or the carboxylic acid derivative is at a main chain of the copolymer.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a resin composition and a molded article. [Background technology]

[0002] Polyamide resins have excellent properties such as resistance to heat deformation, chemical resistance, and abrasion resistance, and are therefore widely used in automobile parts, electrical and electronic parts, industrial materials, etc. In particular, they are widely used in automobile parts such as intake manifolds, radiator tanks, canisters, engine covers, and other engine peripheral parts, as well as heat sinks, connectors, and other battery and motor peripheral parts.

[0003] There is a strong demand for these materials to be lightweight and thin, and materials that combine polyamide with glass fillers (such as glass fibers) are preferably used because they have improved rigidity, as represented by bending strength and bending modulus.

[0004] In these materials, the better the adhesion between the glass filler and the polyamide resin, the greater the effect of improving the rigidity, etc. However, the incorporation of the glass filler reduces the impact resistance, especially the notch strength. It is possible to incorporate an elastomer or a rubber-containing graft copolymer into these materials in order to improve the impact strength, but the incorporation of the conventionally disclosed elastomers and rubber-containing graft copolymers results in a problem of reduced rigidity, such as bending strength.

[0005] Many methods have been proposed for improving the impact resistance of polyamide resins, for example, Patent Document 1 proposes a method of blending an acid-modified ethylene / propylene copolymer (acid-modified EPR) with polyamide, and Patent Document 2 proposes a method of blending an olefin-maleic anhydride copolymer with polyamide resin. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 59-131649 [Patent Document 2] Special Publication No. 2014-503003 Summary of the Invention [Problem to be solved by the invention]

[0007] However, the techniques described in Patent Documents 1 and 2 were insufficient in achieving both rigidity and impact resistance of the glass filler-containing polyamide resin.

[0008] In view of the above-mentioned problems in the prior art, an object of the present invention is to provide a resin composition and a molded article thereof which are excellent in impact resistance and rigidity. [Means for solving the problem]

[0009] That is, the present invention has the following features. [1] A resin composition comprising: a polyamide resin (A); a glass filler (B); and a copolymer (C) of a carboxylic acid and / or a carboxylic acid derivative and an α-olefin having 15 or more carbon atoms, wherein structural units derived from the carboxylic acid and / or the carboxylic acid derivative are present in the main chain of the copolymer (C). [2] The resin composition according to [1], wherein the glass filler (B) is a glass fiber. [3] The resin composition according to [1] or [2], wherein the carboxylic acid and / or carboxylic acid derivative of the copolymer (C) is a dicarboxylic acid anhydride. [4] The resin composition according to any one of [1] to [3], wherein the acid value of the copolymer (C) is 15 mg·KOH / g or more and 200 mg·KOH / g or less. [5] The resin composition according to any one of [1] to [4], wherein the mass average molecular weight of the copolymer (C) is 5,000 or more and 200,000 or less. [6] The resin composition according to any one of [1] to [5], wherein a content of the glass filler (B) is 5 parts by mass or more and 80 parts by mass or less per 100 parts by mass of the polyamide resin (A), the glass filler (B), and the copolymer (C). [7] The resin composition according to any one of [1] to [6], wherein the content of the copolymer (C) is 0.1 parts by mass or more and 10 parts by mass or less in a total of 100 parts by mass of the polyamide resin (A), the glass filler (B), and the copolymer (C). [8] A molded article comprising the resin composition according to any one of [1] to [7]. Effect of the Invention

[0010] According to the present invention, it is possible to provide a glass filler-containing polyamide resin composition having excellent rigidity and impact resistance, and a molded article thereof. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] The following describes in detail the embodiments of the present invention, but the present invention is not limited to these descriptions, and can be modified as appropriate without departing from the spirit of the present invention, except for the following examples. In this specification, "to" includes the lower limit and the upper limit. In addition, for each preferred range, the upper limit and the lower limit can be used in any combination.

[0012] The resin composition according to this embodiment contains a polyamide resin (A), a glass filler (B), and a copolymer (C) of a carboxylic acid and / or a carboxylic acid derivative with an α-olefin.

[0013] [Polyamide resin (A)] The resin composition according to the present embodiment contains a polyamide resin (A). Here, the polyamide resin is a polymer having an amide bond (-NHCO-) ​​in the main chain. The polyamide resin (A) is not particularly limited, but examples thereof include polyamide resins obtained by condensation polymerization of diamines and dicarboxylic acids, polyamide resins obtained by ring-opening polymerization of lactams, polyamide resins obtained by self-condensation of aminocarboxylic acids, and copolymers obtained by copolymerization of two or more monomers constituting these polyamide resins. These may be used alone or in combination of two or more. When used in combination, a method of using these polyamide resins in a blend, a method of using a polyamide resin obtained by copolymerizing the raw materials of these polyamides, and the like may be mentioned.

[0014] The raw materials for the polyamide resin will be described below.

[0015] <Diamine> The diamine is not limited to the following, but examples thereof include aliphatic diamines, alicyclic diamines, and aromatic diamines.

[0016] Examples of the aliphatic diamine include, but are not limited to, linear saturated aliphatic diamines having 2 to 20 carbon atoms, such as ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, and tridecamethylenediamine; and branched saturated aliphatic diamines having 3 to 20 carbon atoms, such as 2-methylpentamethylenediamine (also written as 2-methyl-1,5-diaminopentane), 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 2-methyloctamethylenediamine, and 2,4-dimethyloctamethylenediamine. Examples of the branched saturated aliphatic diamine include diamines having a substituent branched from the main chain.

[0017] Examples of the alicyclic diamine (also referred to as alicyclic diamine) include, but are not limited to, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine, 1,3-cyclopentanediamine, and the like.

[0018] Examples of the aromatic diamine include, but are not limited to, metaxylylenediamine, paraxylylenediamine, metaphenylenediamine, orthophenylenediamine, and paraphenylenediamine.

[0019] <Dicarboxylic acid> The dicarboxylic acid is not limited to the following, but examples thereof include aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and aromatic dicarboxylic acids.

[0020] Examples of the aliphatic dicarboxylic acid include, but are not limited to, linear or branched saturated aliphatic dicarboxylic acids having 3 to 20 carbon atoms, such as malonic acid, dimethylmalonic acid, succinic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylglutaric acid, 2,2-diethylsuccinic acid, 2,3-diethylglutaric acid, glutaric acid, 2,2-dimethylglutaric acid, adipic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, octadecanedioic acid, eicosane dioic acid, and diglycolic acid.

[0021] Examples of the alicyclic dicarboxylic acid include, but are not limited to, alicyclic carboxylic acids such as 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,3-cyclopentanedicarboxylic acid. The number of carbon atoms in the alicyclic structure of the alicyclic carboxylic acid is not particularly limited, but is preferably 3 to 10, and more preferably 5 to 10, from the viewpoint of the balance between the water absorption property and the crystallinity of the resulting polyamide resin.

[0022] The alicyclic dicarboxylic acid may be unsubstituted or may have a substituent. Examples of the substituent include, but are not limited to, alkyl groups having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a tert-butyl group.

[0023] The aromatic dicarboxylic acid is not limited to the following, but examples thereof include unsubstituted or substituted aromatic dicarboxylic acids having 8 to 20 carbon atoms. Examples of the substituent include, but are not limited to, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, a halogen group such as a chloro group or a bromo group, an alkylsilyl group having 3 to 10 carbon atoms, a sulfonic acid group, and a salt thereof such as a sodium salt thereof. Examples of the aromatic dicarboxylic acid include, but are not limited to, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, and 5-sodium sulfoisophthalic acid.

[0024] The dicarboxylic acid may further contain a polyvalent carboxylic acid having a valence of three or more, such as trimellitic acid, trimesic acid, or pyromellitic acid, within the scope of the present embodiment. The above-mentioned diamines and dicarboxylic acids may each be used alone or in combination of two or more kinds.

[0025] <Lactam> Examples of the lactam include, but are not limited to, butyrolactam, pivalolactam, ε-caprolactam, caprylolactam, enantholactam, undecanolactam, and laurolactam (dodecanolactam). Among these, from the viewpoint of toughness, ε-caprolactam, laurolactam, etc. are preferred, and ε-caprolactam is more preferred.

[0026] <Aminocarboxylic acid> The aminocarboxylic acid is not limited to the following, but examples thereof include the above-mentioned lactam ring-opened compounds (ω-aminocarboxylic acid, α,ω-aminocarboxylic acid, etc.). From the viewpoint of increasing the crystallinity of the polyamide resin, the aminocarboxylic acid is preferably a linear or branched saturated aliphatic carboxylic acid having 4 to 14 carbon atoms and substituted with an amino group at the ω-position. Examples of the aminocarboxylic acid include, but are not limited to, 6-aminocaproic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid. Examples of the aminocarboxylic acid include paraaminomethylbenzoic acid.

[0027] Examples of the polyamide resin (A) include, but are not limited to, polyamide 4 (poly-α-pyrrolidone), polyamide 6 (polycaproamide), polyamide 11 (polyundecane amide), polyamide 12 (polydodecanamide), polyamide 46 (polytetramethylene adipamide), polyamide 56 (polypentamethylene adipamide), polyamide 66 (polyhexamethylene adipamide), polyamide 610 (polyhexamethylene sebacamide), polyamide 612 (polyhexamethylene adipamide), polyamide 613 (polyhexamethylene sebacamide), polyamide 614 (polyhexamethylene sebacamide), polyamide 615 (polyhexamethylene sebacamide), polyamide 616 (polyhexamethylene adipamide), polyamide 617 (polyhexamethylene sebacamide), polyamide 618 (polyhexamethylene sebacamide), polyamide 619 (polyhexamethylene sebacamide), polyamide 620 (polyhexamethylene sebacamide), polyamide 621 (polyhexamethylene sebacamide), polyamide 622 (polyhexamethylene sebacamide), polyamide 623 (polyhexamethylene sebacamide), polyamide 624 (polyhexamethylene sebacamide), polyamide 625 (polyhexamethylene sebacamide), polyamide 626 (polyhexamethylene sebacamide), polyamide 627 (polyhexamethylene sebacamide), polyamide 628 (polyhexamethylene sebacamide), polyamide 629 (polyhexamethylene sebacamide), polyamide 630 (polyhexamethylene sebacamide), polyamide 631 (polyhexamethylene sebacamide), polyamide 632 (polyhexamethylene sebacamide), polyamide 633 (polyhexamethylene sebacamide), polyamide 634 (polyhexamethylene sebac polyamide 116 (polyundecamethylene adipamide), polyamide TMHT (trimethylhexamethylene terephthalamide), polyamide 6T (polyhexamethylene terephthalamide), polyamide 2Me-5T (poly 2-methylpentamethylene terephthalamide), polyamide 9T (polynonamethylene terephthalamide), 2Me-8T (poly 2-methyloctamethylene terephthalamide), polyamide 6I (polyhexamethylene isophthalamide), polyamide 6C (polyhexamethylene Polyamide 2Me-5C (Poly 2-methylpentamethylenecyclohexanedicarboxamide), Polyamide 9C (Polynonamethylenecyclohexanedicarboxamide), Polyamide 2Me-8C (Poly 2-methyloctamethylenecyclohexanedicarboxamide), Polyamide PBCM12 (Polybis(4-aminocyclohexyl)methanedecamide), Polyamide dimethyl PBCM12 (Polybis(3-methyl-aminocyclohexyl)methanedecamide), Poly Examples of polyamide resins include amide MXD6 (polymetaxylylene adipamide), polyamide 10T (polydecamethylene terephthalamide), polyamide 11T (polyundecamethylene terephthalamide), polyamide 12T (polydodecamethylene terephthalamide), polyamide 10C (polydecamethylene cyclohexane dicarboxamide), polyamide 11C (polyundecamethylene cyclohexane dicarboxamide), and polyamide 12C (polydodecamethylene cyclohexane dicarboxamide). The "Me" represents a methyl group.

[0028] In addition, when the above-mentioned various monomers are polymerized to produce the polyamide resin (A), a terminal blocking agent can be further added to adjust the molecular weight. The terminal blocking agent is not particularly limited, and any known agent can be used.

[0029] Examples of the end-capping agent include, but are not limited to, monocarboxylic acids, monoamines, acid anhydrides, monoisocyanates, monoacid halides, monoesters, and monoalcohols. These may be used alone or in combination of two or more.

[0030] Monocarboxylic acids that can be used as end-capping agents may be any that are reactive with amino groups, and include, but are not limited to, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, and isobutyric acid; alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid; and aromatic monocarboxylic acids such as benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylacetic acid. These may be used alone or in combination of two or more.

[0031] The monoamine that can be used as the end-capping agent may be any monoamine that is reactive with a carboxyl group, and includes, but is not limited to, aliphatic monoamines such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, and dibutylamine; alicyclic monoamines such as cyclohexylamine and dicyclohexylamine; aromatic monoamines such as aniline, toluidine, diphenylamine, and naphthylamine; and the like. These may be used alone or in combination of two or more.

[0032] Examples of acid anhydrides that can be used as end-capping agents include, but are not limited to, phthalic anhydride, maleic anhydride, benzoic anhydride, acetic anhydride, and hexahydrophthalic anhydride. These may be used alone or in combination of two or more.

[0033] Examples of monoisocyanates that can be used as an end-capping agent include, but are not limited to, phenyl isocyanate, tolyl isocyanate, dimethylphenyl isocyanate, cyclohexyl isocyanate, butyl isocyanate, and naphthyl isocyanate. These may be used alone or in combination of two or more.

[0034] Examples of monoacid halides that can be used as end-capping agents include, but are not limited to, halogen-substituted monocarboxylic acids such as monocarboxylic acids such as benzoic acid, diphenylmethanecarboxylic acid, diphenylsulfonecarboxylic acid, diphenylsulfoxidecarboxylic acid, diphenylsulfidecarboxylic acid, diphenylethercarboxylic acid, benzophenonecarboxylic acid, biphenylcarboxylic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, and anthracenecarboxylic acid. These may be used alone or in combination of two or more.

[0035] Examples of monoesters that can be used as end-capping agents include, but are not limited to, glycerin monopalmitate, glycerin monostearate, glycerin monobehenate, glycerin monomontanate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol monobehenate, pentaerythritol monomontanate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monobehenate, sorbitan monomontanate, sorbitan dimontanate, sorbitan trimontanate, sorbitol monopalmitate, sorbitol monostearate, sorbitol monobehenate, sorbitol tribehenate, sorbitol monomontanate, and sorbitol dimontanate. These may be used alone or in combination of two or more.

[0036] Examples of monoalcohols that can be used as end-capping agents include, but are not limited to, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, docosanol, tricosanol, tetracosanol, hexacosanol, heptacosanol, octacosanol, triacontanol (all of which are linear and branched), oleyl alcohol, behenyl alcohol, phenol, cresol (o-, m-, p-isomer), biphenol (o-, m-, p-isomer), 1-naphthol, and 2-naphthol. These may be used alone or in combination of two or more.

[0037] The terminal group of the polyamide resin (A) used in this embodiment is not particularly limited, but generally includes an amino group or a carboxy group. The molar ratio of the amount of amino terminal groups to the amount of carboxy terminal groups in the polyamide resin (A) (molar amount of amino terminal groups / molar amount of carboxy terminal groups) is not particularly limited, but is preferably 0.05 to 1.5, more preferably 0.1 to 1.0, and even more preferably 0.15 to 0.7. When the molar ratio of the amount of terminal groups is 0.05 or more, the reaction between the polyamide resin (A) and the rubber-containing graft polymer (B) containing an epoxy group and the copolymer (C) containing a carboxy group and / or a derivative thereof during melt kneading becomes good, and the impact resistance tends to be good. In addition, when the molar ratio of the amount of terminal groups is 1.5 or less, the heat deterioration resistance of the molded article obtained from the resin composition tends to be better.

[0038] The molar amount of the amino terminal group of the polyamide is not particularly limited, but is preferably 10 to 100 μmol / g, more preferably 15 to 80 μmol / g, and even more preferably 30 to 80 μmol / g. When the amount of the amino terminal group is within the above range, the impact resistance of the resin composition tends to be more excellent.

[0039] Here, examples of methods for measuring the amount of amino end groups and the amount of carboxyl end groups in this specification include 1H-NMR and titration. In the 1H-NMR method, the amount can be determined from the integral value of the characteristic signal corresponding to each end group. In the titration method, for the amino end groups, a method of titrating a phenol solution of a polyamide resin with 0.1N hydrochloric acid, and for the carboxyl end groups, a method of titrating a benzyl alcohol solution of a polyamide resin with 0.1N sodium hydroxide, etc. can be used.

[0040] The method for adjusting the concentration of the terminal groups of the polyamide is not particularly limited, but may be, for example, the above-mentioned method using the terminal blocking agent.

[0041] [Glass filler (B)]

[0042] In this embodiment, the filler means a component that is added for the purpose of imparting mechanical strength, light reflection / scattering, flame retardancy, sound insulation, vibration damping, etc., and has a melting point equal to or higher than the processing temperature of the thermoplastic resin used. As the filler, a glass filler mainly composed of silicate is preferable, and examples thereof include layered silicate, talc, mica, porous particles such as silica, and glass (glass fiber, milled glass, glass flakes, glass beads, etc.). From the viewpoint of the bending properties (rigidity) of the molded product, glass fiber is particularly preferable. In addition, the resin composition containing glass fiber can be colored in any color by using a pigment or dye in combination.

[0043] The average fiber diameter of the glass fibers is not particularly limited, but from the viewpoint of the bending properties (rigidity) of the molded product, it is preferably 1 to 100 μm or more, more preferably 2 to 50 μm or more, and even more preferably 3 to 30 μm or more.

[0044] [Copolymer (C)] The resin composition according to the present embodiment contains a copolymer (C) of a carboxylic acid and / or a carboxylic acid derivative and an α-olefin, the main chain of which contains a structural unit derived from a carboxylic acid and / or a carboxylic acid derivative. The copolymer (C) may contain other components such as a diene.

[0045] The carboxylic acid is not particularly limited, but examples thereof include (meth)acrylic acid, maleic acid, methylmaleic acid, fumaric acid, methylfumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, glutaconic acid, norbornane-5-ene-2,3-dicarboxylic acid, etc. Here, "(meth)acrylic acid" refers to acrylic acid or methacrylic acid.

[0046] The carboxylic acid derivative is not particularly limited, and examples thereof include carboxylic acid esters, carboxylic acid anhydrides, and carboxylic acid imides.

[0047] The carboxylic acid ester is not particularly limited, and examples thereof include ester compounds of the above-mentioned carboxylic acids, such as (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and glycidyl (meth)acrylate.

[0048] The carboxylic acid anhydride is not particularly limited, and examples thereof include anhydrides of the above-mentioned carboxylic acids. Preferred examples include dicarboxylic acid anhydrides such as maleic anhydride, itaconic anhydride, succinic anhydride, citraconic anhydride, and 5-norbornene-2,3-dicarboxylic anhydride.

[0049] The carboxylic acid imide is not particularly limited, and examples thereof include imide compounds of the above-mentioned carboxylic acids, such as maleimide compounds such as maleimide, N-ethylmaleimide, and N-phenylmaleimide.

[0050] These may be used alone or in combination of two or more. Among the above, from the viewpoint of copolymerization reactivity, carboxylic acid esters or dicarboxylic acid anhydrides are preferred, dicarboxylic acid anhydrides are more preferred, and maleic anhydride is particularly preferred.

[0051] When maleic anhydride is selected as the carboxylic acid derivative, the copolymer (C) has the following general formula as a constituent unit. [ka]

[0052] In the formula, at least one of R1, R2, R3, and R4 is an alkyl group having one or more carbon atoms, the others are hydrogen atoms, and x and y are integers of 1 or more.

[0053] The method for producing the copolymer (C) is not particularly limited, and examples thereof include (1) a method of polymerizing an α-olefin resin and then adding a compound or monomer having a carboxylic acid and / or a carboxylic acid derivative, and (2) a method of copolymerizing an α-olefin with a compound or monomer having a carboxylic acid and / or a carboxylic acid derivative. As the polymerization method, radical polymerization methods such as solution polymerization, emulsion polymerization, suspension polymerization, and bulk polymerization, or living polymerization methods can be adopted. Furthermore, a method of polymerizing after forming a macromonomer once can also be adopted. In terms of ease of obtaining a polymer having a carboxylic acid and / or a carboxylic acid derivative in the main chain, the method (2) of copolymerizing an α-olefin with a compound or monomer having an acidic group is preferred.

[0054] The total proportion of carboxylic acids and carboxylic acid derivatives in 100 mol% of copolymer (C) is not particularly limited, but in order to improve the adhesion between the glass filler (B) and the polyamide resin (A), it is preferably 20 mol% or more, and more preferably 30 mol% or more, while in order to improve the appearance of the molded article, it is preferably 80 mol% or less, and more preferably 70 mol% or less.

[0055] Although there is no particular limitation on the α-olefin, it is preferable that the resin composition contains an α-olefin having 15 or more carbon atoms. When an α-olefin having 15 or more carbon atoms is contained, the resin composition can achieve both rigidity and impact resistance. In 100% by mass of the α-olefin, the α-olefin having 15 or more carbon atoms is preferably contained in an amount of 0.5% by mass or more, more preferably 1% by mass or more, and particularly preferably 2% by mass or more. The number of carbon atoms of the α-olefin is preferably 20 or more, more preferably 24 or more, even more preferably 25 or more, particularly preferably 26 or more, and most preferably 30 or more. On the other hand, in terms of dispersibility in resin, the number of carbon atoms of the α-olefin is preferably 150 or less, more preferably 130 or less, even more preferably 100 or less, even more preferably 80 or less, and particularly preferably 60 or less.

[0056] The number of carbon atoms and the content of the α-olefin can be determined by dissolving the copolymer (C) in THF and subjecting the solution to pyrolysis GC-MS (gas chromatography mass spectrometer, using a non-polar column) to obtain the molecular weight, and the number of carbon atoms and the content of the α-olefin can be calculated from the obtained molecular weight.

[0057] The proportion of α-olefin units in 100 mol% of copolymer (C) is not particularly limited, but in order to improve the compatibility between the polyester resin and the polyolefin resin, it is preferably 20 mol% or more, and more preferably 30 mol% or more, while in order to improve the appearance of the molded product, it is preferably 80 mol% or less, and more preferably 70 mol% or less.

[0058] The acid value of the copolymer (C) is preferably 15 mg KOH / g or more, more preferably 30 mg KOH / g or more, more preferably 50 mg KOH / g or more, even more preferably 60 mg KOH / g or more, and particularly preferably 70 mg KOH / g or more, in order to improve the adhesion between the glass filler (B) and the polyamide resin (A) and to improve the impact resistance and rigidity of the molded body. On the other hand, if the acid value of the copolymer (C) is too high, the copolymer (C) may react excessively with the amino group at the end of the polyamide resin (A), and the impact resistance of the molded body may decrease. Therefore, from the viewpoint of the impact resistance of the molded body, the acid value is preferably 200 mg KOH / g or less, more preferably 150 mg KOH / g or less, even more preferably 120 mg KOH / g or less, and particularly preferably 100 mg KOH / g or less. The acid value of copolymer (C) can be measured by titration. 2.0 g of copolymer (C) is dissolved in a solvent (ethanol / toluene 3 / 7 mixture) at 90°C. After cooling, 3 drops of phenolphthalein solution are added to the solution, and then titrated with 0.5 mol / L KOH ethanol solution to obtain the acid value.

[0059] The mass average molecular weight of the copolymer (C) is not particularly limited, but from the viewpoint of impact resistance and rigidity, it is preferably 2,000 or more, more preferably 3,000 or more, and even more preferably 5,000 or more, while it is preferably 200,000 or less, more preferably 100,000 or less, even more preferably 50,000 or less, and most preferably 30,000 or less. The mass average molecular weight of the copolymer (C) may be, for example, 2,000 or more and 50,000 or less, 3,000 or more and 30,000 or less, or 5,000 or more and 200,000 or less. The mass average molecular weight of the copolymer (C) is a value calculated in terms of standard polystyrene, which is measured by dissolving the copolymer (C) in tetrahydrofuran (THF) and performing gel permeation chromatography.

[0060] An example of a commercially available product of the copolymer (C) is Diacalna 30M (manufactured by Mitsubishi Chemical Corporation).

[0061] [Resin composition] In the resin composition of the present embodiment, the proportion of the polyamide resin (A) in a total of 100 parts by mass of the polyamide resin (A), the glass filler (B) and the copolymer (C) is preferably 10 to 90 parts by mass, more preferably 35 to 85 parts by mass, and particularly preferably 47 to 80 parts by mass. If the content of the polyamide resin (A) is 10 parts by mass or more, the molded article of the resin composition can have sufficient bending properties (rigidity), and if it is 90 parts by mass or less, the balance between impact strength and rigidity is sufficient.

[0062] In the resin composition of the present embodiment, the proportion of the glass filler (B) in a total of 100 parts by mass of the polyamide resin (A), the glass filler (B) and the copolymer (C) is preferably 5 to 80 parts by mass, more preferably 10 to 60 parts by mass, and particularly preferably 20 to 50 parts by mass. If the content of the glass filler (B) is 5 parts by mass or more, the molded article of the resin composition can have sufficient bending properties (rigidity), and if it is 80 parts by mass or less, the balance between impact strength and rigidity is sufficient.

[0063] Furthermore, in the resin composition of this embodiment, the proportion of copolymer (C) in a total of 100 parts by mass of polyamide resin (A), glass filler (B) and copolymer (C) is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, and particularly preferably 0.1 to 3 parts by mass. If the content of copolymer (C) is 0.1 part by mass, the adhesion between polyamide resin (A) and glass filler (B) can be improved, and if it is 10 parts by mass or less, a sufficient balance between impact resistance and rigidity can be achieved.

[0064] The resin composition may contain other components in addition to the polyamide resin (A), the glass filler (B), and the copolymer (C).

[0065] Examples of other components include resins other than polyamide, flame retardants (phosphorus-based, bromine-based, silicone-based, organic metal salt-based, etc.), drip prevention agents (e.g., fluorinated polyolefin, silicone, and aramid fiber), lubricants (e.g., long-chain fatty acid metal salts such as magnesium stearate, etc.), release agents (e.g., pentaerythritol tetrastearate, etc.), nucleating agents, antistatic agents, stabilizers (e.g., phenol-based stabilizers, sulfur-based stabilizers, phosphorus-based stabilizers, ultraviolet absorbers, amine-based light stabilizers, etc.), plasticizers, dyes, pigments, etc. Note that these other components can be well-known materials, and can be arbitrarily selected and used according to the application of the resin composition, and each other component in the resin composition can also be arbitrarily selected.

[0066] The proportion of other components in 100 parts by mass of the resin composition is not particularly limited, but is usually 0.1 parts by mass or more, and preferably 60 parts by mass or less, and more preferably 50 parts by mass or less.

[0067] Any method may be used to produce the resin composition. For example, the polyamide resin (A), the glass filler (B), the copolymer (C), and other components, if necessary, are thoroughly mixed using a premixing means such as a V-type blender, a Henschel mixer, a mechanochemical device, or an extrusion mixer, and then granulated using an extrusion granulator or a briquetting machine, and then melt-kneaded and extruded using a melt mixer.

[0068] Examples of the melt kneader include twin-screw extruders such as vented twin-screw extruders, Banbury mixers, kneading rolls, single-screw extruders, and multi-screw extruders having three or more screws. The temperature during melt kneading is, for example, 200 to 320° C. The resin composition extruded as described above is directly cut and pelletized by a device such as a pelletizer, or cooled to form strands, and then the strands are cut and pelletized by a device such as a pelletizer.

[0069] The resin composition can be molded to obtain a molded article. Examples of applications of the resin composition include molded articles useful in automobile parts, electric and electronic parts, industrial materials, and other fields. EXAMPLES

[0070] The present invention will be specifically described below with reference to examples. However, the present invention is not limited to the following examples. In the following examples, % is by weight unless otherwise specified.

[0071] [Example 1, Comparative Examples 1 to 5] The polyamide resin (A) and the copolymer (C) were blended in the ratio shown in Table 1 and mixed by hand blending. Then, using a φ35 mm counter-rotating twin screw extruder, the mixture was melt-kneaded while side-feeding a specified amount of glass filler (B) at a screw rotation speed of 100 rpm and a cylinder temperature of 240 to 260°C to obtain a resin composition. The obtained resin composition was injection molded using a 100t injection molding machine under conditions of a molding temperature of 240 to 260°C and a mold temperature of 80°C to obtain molded bodies of 80 mm length x 10 mm width x 4 mm thickness. The obtained molded bodies were then annealed under room temperature / humidity control conditions for one week or more, and the following evaluations were carried out using each molded body. The obtained results are shown in Table 1.

[0072] [Example 2, Comparative Examples 6 to 10] Polyamide resin (A) and copolymer (C) were blended in the ratio shown in Table 2 and mixed by hand blending. Then, using a φ35 mm counter-rotating twin screw extruder, the mixture was melt-kneaded while side-feeding a specified amount of glass filler (B) at a screw rotation speed of 100 rpm and a cylinder temperature of 270 to 290°C to obtain a resin composition. The obtained resin composition was injection molded using a 100t injection molding machine under conditions of a molding temperature of 270 to 290°C and a mold temperature of 80°C to obtain molded bodies of 80 mm length x 10 mm width x 4 mm thickness. The obtained molded bodies were then annealed under room temperature / humidity control conditions for one week or more, and the following evaluations were carried out using each molded body. The obtained results are shown in Table 2.

[0073] The details of each ingredient shown in Tables 1 and 2 are as follows: (Polyamide resin (A-1)) EPR27 (Shenma, polyamide 66) (Polyamide resin (A-2)) UBE Nylon 1013B (UBE Corporation, Polyamide 6) (Glass filler (B)) ECS301CL-4.5H (manufactured by Chongqing International Composites Co., Ltd. (CPIC), fiber length 4.5mm, diameter 10μm) (Copolymer (C-1)) Diacaluna 30M (manufactured by Mitsubishi Chemical Corporation, an alternating copolymer of α-olefins with 28 to 58 carbon atoms and maleic anhydride, acid value 80 mg KOH / g, mass average molecular weight 10,000) (Copolymer (C-2)) ZeMac EP-60 (Vertellus, alternating copolymer of ethylene and maleic anhydride, acid value 444 mg KOH / g, mass average molecular weight 60,000) (Copolymer (C-3)) Hiwax 1105A (Mitsui Chemicals, Inc., maleic anhydride modified polyethylene, acid value 60 mg KOH / g, mass average molecular weight 1,500) (Copolymer (C-4)) Modic P908 (manufactured by Mitsubishi Chemical Corporation, maleic anhydride modified polyolefin, acid value 10 mg KOH / g, mass average molecular weight 150,000)

[0074] [Charpy impact test] The measurements were made in accordance with ISO-179-1 and with a TYPE A notch in accordance with ISO 2818. The measurements were performed at 23°C.

[0075] [Bending test] The measurements were performed in accordance with ISO-178 at 23°C.

[0076] [Table 1]

[0077] [Table 2]

[0078] As can be seen by comparing Example 1 with Comparative Example 1, and Example 2 with Comparative Example 6, in a resin composition containing a polyamide resin (A) and a glass filler (B), by using in combination a copolymer (C-1) which is a copolymer of a carboxylic acid and / or a carboxylic acid derivative and an α-olefin and has a structural unit derived from a carboxylic acid and / or a carboxylic acid derivative in its main chain, it is possible to obtain a molded product in which the Charpy impact strength, which is an index of impact resistance, and the flexural strength and flexural modulus, which are indexes of rigidity, are both significantly improved.

[0079] Furthermore, as can be seen by comparing Example 1 with Comparative Examples 2 and 3, when a copolymer (C-1) containing an α-olefin having 15 or more carbon atoms is used in combination, a molded product having excellent impact strength and rigidity can be obtained.

[0080] Furthermore, as can be seen by comparing Example 1 with Comparative Examples 4-5, and Example 2 with Comparative Examples 7-10, when copolymers (C-3, C-4) having carboxylic acid and / or carboxylic acid derivative in the graft chain rather than in the main chain are used in combination, molded articles having insufficient impact strength and rigidity are obtained, whereas when copolymers (C-1) having carboxylic acid and / or carboxylic acid derivative in the main chain are used in combination, molded articles having excellent impact strength and rigidity are obtained. [Industrial Applicability]

[0081] One aspect of the present invention can be used in automobile parts, electronic device parts, and the like.

Claims

1. A polyamide resin (A), A glass filler (B); The copolymer (C) contains a carboxylic acid and / or a carboxylic acid derivative and an α-olefin having 15 or more carbon atoms, A resin composition, wherein the structural unit derived from the carboxylic acid and / or a carboxylic acid derivative is present in the main chain of the copolymer (C).

2. The resin composition according to claim 1 , wherein the glass filler (B) is a glass fiber.

3. The resin composition according to claim 1 , wherein the carboxylic acid and / or carboxylic acid derivative of the copolymer (C) is a dicarboxylic acid anhydride.

4. The resin composition according to claim 1, wherein the acid value of the copolymer (C) is 15 mg·KOH / g or more and 200 mg·KOH / g or less.

5. The resin composition according to claim 1, wherein the mass average molecular weight of the copolymer (C) is 5,000 or more and 200,000 or less.

6. 2. The resin composition according to claim 1, wherein a content of the glass filler (B) in a total of 100 parts by mass of the polyamide resin (A), the glass filler (B), and the copolymer (C) is 5 parts by mass or more and 80 parts by mass or less.

7. 2. The resin composition according to claim 1, wherein a content of the copolymer (C) in a total of 100 parts by mass of the polyamide resin (A), the glass filler (B), and the copolymer (C) is 0.1 parts by mass or more and 10 parts by mass or less.

8. A molded article comprising the resin composition according to any one of claims 1 to 7.

Images