JPWO2018216770A1 - Glass fiber reinforced polyamide resin composition - Google Patents

Abstract

A glass fiber reinforced polyamide resin composition having less black discoloration, no floatation of glass fibers and the like, and excellent weather resistance even under use conditions exposed to rainfall, comprising a crystalline aliphatic polyamide resin (A), Amorphous polyamide resin (B), acrylic resin (C), mica (D), glass fiber (E), carbon black (F), hindered amine light stabilizer (G), and ultraviolet absorber (H) (10-40): (2-20): (1-10): (2-25): (20-50): (0.1-5): (0.05-1.0): (0 To 1.0), and when the total content of the components (A) to (H) is 100 parts by mass, the copper compound (I) is contained in an amount of 0.005 to 1.0 part by mass. It is a glass fiber reinforced polyamide resin composition contained in a proportion.

Description

  The present invention is a glass fiber reinforced polyamide resin which is excellent in molded article appearance, has little black discoloration, does not float fillers such as glass fibers, and has excellent weatherability even under the use conditions exposed to rain, especially outdoors. Composition.

  Polyamide resins are widely used for parts such as automobiles and electric / electronic products because of their excellent mechanical properties, thermal properties and chemical resistance. In addition, a reinforced polyamide resin composition in which glass fiber is blended with a polyamide resin greatly improves mechanical properties, heat resistance, chemical resistance, etc., and is reinforced as a metal substitute material from the viewpoint of weight reduction and rationalization of processes. The use of polyamide resin compositions has been actively studied.

  A reinforced polyamide resin composition containing a high concentration of glass fiber, wollastonite, etc., can easily provide molded articles with high rigidity, but has the disadvantage of poor weather resistance and is improved for use outdoors. is necessary. As methods for improving such weather resistance, for example, Patent Documents 1 to 3 have been proposed.

  Patent Literature 1 proposes blending an acrylic resin and an epoxy group-containing compound with polymethaxylylene adipamide. However, in this method, since the epoxy group-containing compound is indispensable, if there is a stagnation at the time of molding, there is a disadvantage that the appearance of the molded article is impaired due to the occurrence of a gel-like substance or a decrease in melt fluidity. The weather resistance was also insufficient. Patent Literature 2 proposes that a crystalline semi-aromatic polyamide is mainly used and glass fiber, wollastonite, carbon black, and a copper compound are contained. Since such a resin composition is mainly composed of semi-aromatic polyamide, it is necessary to increase the molding resin temperature, and since wollastonite is blended, there are disadvantages in production such as the problem of screw abrasion cannot be avoided. In addition, when mica was added instead of wollastonite, the effect of fading black after weathering exposure and improving weatherability was insufficient, and there was room for improvement. Patent Literature 3 proposes mainly containing a crystalline semi-aromatic polyamide and containing glass fiber, wollastonite, a specific carbon black, and a copper compound. Such a resin composition also has the same drawbacks as in Patent Document 2, and it is necessary to use a specific carbon black. If the resin composition is mainly composed of an aliphatic polyamide, the discoloration of black after weathering exposure and the effect of improving weathering resistance are poor. It was enough and there was room for improvement.

Japanese Patent No. 3442502 JP 2000-273299 A JP-A-2002-284990

  The present invention has been made in view of the above-mentioned state of the art, and its object is to provide a molded article having excellent appearance, outdoors, especially under use conditions exposed to rain, with little black discoloration, glass fiber. It is an object of the present invention to provide a glass fiber reinforced polyamide resin composition having excellent weather resistance, in which a filler such as a filler does not float.

  The present inventor has conducted intensive studies to achieve such an object, and as a result, has found that crystalline aliphatic polyamide resin, amorphous polyamide resin, acrylic resin, mica, glass fiber, carbon black, and hindered amine light The present inventors have found that a glass fiber reinforced polyamide resin composition having excellent weather resistance can be provided by blending a stabilizer, an ultraviolet absorber, and a copper compound in a specific ratio, and have completed the present invention.

That is, the present invention employs the following configuration.
(1) Crystalline aliphatic polyamide resin (A), amorphous polyamide resin (B), acrylic resin (C), mica (D), glass fiber (E), carbon black (F), hindered amine light stabilizer (G) and the ultraviolet absorber (H) were (10-40): (2-20): (1-10): (2-25): (20-50): (0.1-5), respectively. : (0.05 to 1.0): contained in a mass ratio of (0 to 1.0), and when the total content of the components (A) to (H) was 100 parts by mass, a copper compound ( A glass fiber reinforced polyamide resin composition comprising I) in an amount of 0.005 to 1.0 part by mass.
(2) The glass fiber reinforced polyamide resin composition according to (1), wherein the amorphous polyamide resin (B) is a semi-aromatic polyamide.
(3) The flat plate obtained by injection molding from the glass fiber reinforced polyamide resin composition has a color difference ΔE before and after a weathering test according to JIS-K-7350-2 of 8.0 or less. The glass fiber reinforced polyamide resin composition according to (1) or (2).
(4) A molded article for vehicle interior or vehicle exterior, which is molded using the glass fiber reinforced polyamide resin composition according to any one of (1) to (3).
(5) A group consisting of an outer handle, an outer door handle, a wheel cap, a roof rail, a door mirror base, a room mirror arm, a sunroof deflector, a radiator fan, a radiator grill, a bearing retainer, a console box, a sun visor arm, a spoiler, and a sliding door rail cover. The molded article for vehicle interior or vehicle exterior according to (4), which is selected from the group consisting of:

  The glass fiber reinforced polyamide resin composition of the present invention provides a molded article excellent in weather resistance, which has little black discoloration and has no floating of a filler such as glass fiber even under use conditions exposed to rainfall. Can be.

  The glass fiber reinforced polyamide resin composition of the present invention comprises a crystalline aliphatic polyamide resin (A), an amorphous polyamide resin (B), an acrylic resin (C), a mica (D), a glass fiber (E), and a carbon fiber. Black (F), hindered amine light stabilizer (G), and ultraviolet absorber (H) were respectively (10-40): (2-20): (1-10): (2-25): (20-50) ): (0.1 to 5): (0.05 to 1.0): (0 to 1.0) in a mass ratio, and the total content of the components (A) to (H) is 100 In the case where it is a mass part, the copper compound (I) is contained in a ratio of 0.005 to 1.0 mass part.

  Examples of the crystalline aliphatic polyamide resin (A) include a polyamide resin obtained by polycondensation of lactam, ω-aminocarboxylic acid, dicarboxylic acid, diamine, or the like as a raw material, or a copolymer or blend thereof. Can be Examples of lactams and ω-aminocarboxylic acids include ε-caprolactam, 6-aminocaproic acid, ω-enantholactam, 7-aminoheptanoic acid, 11-aminoundecanoic acid, 9-aminononanoic acid, α-pyrrolidone, α-piperidine And the like. Examples of dicarboxylic acids include glutaric acid, adipic acid, azelaic acid, sebacic acid, and suberic acid, and examples of diamines include tetramethylene diamine, hexamethylene diamine, octamethylene diamine, undecamethylene diamine, and dodecamethylene diamine. No. As specific examples of the crystalline aliphatic polyamide resin (A), polyamide 6, polyamide 12, polyamide 66, polyamide 46, polyamide 610, polyamide 612, and polyamide 1010 are preferable.

  The compounding ratio of the crystalline aliphatic polyamide resin (A) is such that the total content of the component (A) and the components (B) to (H) described later in the glass fiber reinforced polyamide resin composition of the present invention is 100 parts by mass. In this case, the amount is 10 to 40 parts by mass, preferably 20 to 30 parts by mass. If the blending ratio of the crystalline aliphatic polyamide resin (A) is less than the above range, it becomes difficult to melt-extrude the composition, while if it exceeds the above range, mechanical properties, thermal properties, and the like become poor. Tend.

  The amorphous polyamide resin (B) is a polyamide resin having no crystal melting peak in a thermogram measured at a heating rate of 20 ° C./min and measured by DSC. Terephthalic acid, isophthalic acid, adipic acid, sebacic acid, and the like. Examples of the diamine include tetramethylene diamine, hexamethylene diamine, metaxylylenediamine, paraxylylenediamine, undecamethylenediamine, dodecamethylenediamine, and 2-diamine. Examples include methylpentamethylenediamine, trimethylhexamethylenediamine, aminoethylpiperazine, bisaminomethylcyclohexane, and the like. Of these, semi-aromatic polyamides are preferred in order to simultaneously satisfy high flexural modulus and high impact resistance. As the semi-aromatic polyamide, polyamide 6T / 6I using terephthalic acid, isophthalic acid, and hexamethylenediamine as raw materials, polyamide 6T / 66 using terephthalic acid, adipic acid, and hexamethylenediamine as raw materials are preferable.

  The compounding ratio of the amorphous polyamide resin (B) is 100% of the total content of the components (A) and (B) and the components (C) to (H) described later in the glass fiber reinforced polyamide resin composition of the present invention. When it is a mass part, it is 2-20 mass parts, preferably 10-15 mass parts. If the compounding ratio of the amorphous polyamide resin (B) is less than the above range, the appearance of the molded article will be poor, while if it exceeds the above range, poor mold release from the mold and the appearance of the molded article will be poor. Failure tends to occur.

  The compounding ratio of the crystalline aliphatic polyamide resin (A) and the amorphous polyamide resin (B) allows a high elastic modulus to be exhibited, a solidification speed to be adjusted, a strand property during production, and a mold transfer during injection molding. From the viewpoint of improving the properties, a mass ratio of (A) :( B) = 55: 45 to 95: 5 is preferable, and a mass ratio of (A) :( B) = 60: 40 to 95: 5 is more preferable, A mass ratio of (A) :( B) = 60: 40 to 90:10 is more preferable.

  As described above, by adding the amorphous polyamide resin (B) to the crystalline aliphatic polyamide resin (A), the effect of improving the weather resistance is increased. It is presumed that this is because the dispersibility and compatibility of the acrylic resin (C) change.

  Examples of the acrylic resin (C) include a homopolymer or a copolymer of a methacrylic acid ester. The copolymer preferably contains methacrylic acid ester in an amount of 50% by mass or more, more preferably 70% by mass or more. Specific examples of the methacrylate monomer include alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, and butyl methacrylate, β-hydroxyethyl methacrylate, and N, N-dimethylaminoethyl. Examples thereof include methacrylic acid alkyl ester derivatives in which hydrogen of an alkyl group is substituted with a hydroxyl group, an amino group, or the like, such as methacrylate. Examples of the monomer copolymerized with these methacrylic acid ester monomers include vinyl monomers such as methyl acrylate, styrene, α-methylstyrene, and acrylonitrile. Among these acrylic resins (C), particularly preferred is polymethyl methacrylate or polyethyl methacrylate.

  Regarding the melt fluidity of the acrylic resin (C), the melt flow rate (MFR) under the condition of 230 ° C. and 37.3 N is preferably 5 or more, more preferably 15 or more.

  The mixing ratio of the acrylic resin (C) is 100 parts by mass based on the total content of the components (A) to (C) and the components (D) to (H) described below in the glass fiber reinforced polyamide resin composition of the present invention. In this case, the amount is 1 to 10 parts by mass, preferably 1 to 7 parts by mass, more preferably 2 to 7 parts by mass, and still more preferably 3 to 7 parts by mass. If the blending ratio of the acrylic resin (C) is less than the above range, the weather resistance specification cannot be satisfied. On the other hand, if the blending ratio exceeds the above range, poor appearance due to poor mold release or insufficient fluidity, and poor molded product quality. Inability to meet strength specifications.

  In the glass fiber reinforced polyamide resin composition of the present invention, the blending ratio of the acrylic resin (C) is preferably 2 to 30 parts by mass based on 100 parts by mass of the total of the polyamide resins (A) and (B). When the blending ratio of the acrylic resin (C) is less than the above range, the effect of improving the weather resistance decreases, while when it exceeds the above range, the strength, rigidity, solvent resistance, and heat resistance tend to decrease. is there.

  Mica (D) includes muscovite, phlogopite, biotite, artificial mica and the like, and any of them may be used. When the shape of mica is approximated to an ellipse and the average of the major axis and the minor axis is the particle diameter, the particle diameter of mica is preferably about 1 to 30 μm from the balance between appearance and rigidity.

  The mixing ratio of the mica (D) was such that the total content of the components (A) to (D) and the components (E) to (H) described later in the glass fiber reinforced polyamide resin composition of the present invention was 100 parts by mass. In this case, it is 2 to 25 parts by mass, preferably 15 to 22 parts by mass. If the mixing ratio of mica (D) is less than the above range, the effect of improving the appearance of the molded article will be small, while if it exceeds the above range, fluidity and mechanical strength tend to be inferior.

  The cross section of the glass fiber (E) may be circular or flat. Examples of the flat cross-section glass fiber include those having a substantially elliptical shape, a substantially oval shape, and a substantially cocoon shape in a cross section perpendicular to the length direction of the fiber, and having a flatness of 1.5 to 8, and further 2 to 5 It is preferred that Here, the flatness is assumed to be a rectangle having a minimum area circumscribing a cross section perpendicular to the longitudinal direction of the glass fiber, and the length of the long side of the rectangle is defined as the major axis, and the length of the short side is defined as the minor axis. This is the ratio of the major axis / minor axis in the case of the above. If the flatness is less than the above range, the impact resistance of the molded product may not be significantly improved because there is no significant difference in shape from the glass fiber having a circular cross section. On the other hand, when the flatness exceeds the above range, the bulk density in the polyamide resin becomes high, so that it cannot be uniformly dispersed in the polyamide resin, and the impact resistance of the molded product may not be improved much. In the present invention, when glass fibers having a substantially oval cross section and a flatness of 2 to 5 are used, higher mechanical properties can be exhibited.

  The compounding ratio of the glass fiber (E) is the same as the components (A), (B), (C), (D), and (E) in the glass fiber reinforced polyamide resin composition of the present invention, and (F), ( When the total content of the components G) and (H) is 100 parts by mass, the amount is 20 to 50 parts by mass, preferably 25 to 45 parts by mass. If the blending ratio of the glass fiber (E) is less than the above range, the rigidity of the molded product is insufficient, while if it exceeds the above range, the reinforcing effect corresponding to the blending amount tends not to be exhibited.

  In producing the glass fiber reinforced polyamide resin composition of the present invention, particularly when a flat cross-section glass fiber is used, the polyamide-reactive silane coupling agent is used in an amount of 0.1 to 1.0% by mass of the glass fiber (E). It is preferable to add in a ratio. The sizing agent for chopped strands for polyamide contains a small amount of a silane coupling agent in advance in the fiber bundle in order to improve the adhesion to the matrix resin. However, since the amount of the aminosilane coupling agent that can be attached to the fiber bundle in advance has an upper limit so that the fiber bundle does not cause defibration failure during extrusion, it is preferable to add an insufficient amount.

Examples of the carbon black (F) include, but are not particularly limited to, thermal black, channel black, acetylene black, Ketjen black, furnace black, and the like. It is preferable that the average particle diameter is in the range of 10 to 40 μm, the specific surface area by the BET adsorption method is in the range of 50 to 300 m ² / g, and the measured oil absorption using dibutyl phthalate is in the range of 50 cc / 100 g to 150 cc / 100 g. It is.

  It is preferable in terms of workability that the carbon black (F) is blended as a master batch using a polyethylene resin or a polystyrene resin as a base resin. Examples of the base resin include various polyethylenes represented by low-density polyethylene (LDPE), high-density polyethylene (HDPE), ultrahigh-molecular-weight polyethylene (UHMWPE), etc., and random copolymers and block copolymers of ethylene-propylene, Copolymers of ethylene and α-olefins such as random copolymers and block copolymers of ethylene-butene, ethylene-methacrylates, copolymers of ethylene and unsaturated carboxylic acid esters such as ethylene-butyl acrylate, ethylene A polyethylene resin such as a copolymer of ethylene and an aliphatic vinyl such as vinyl acetate, a homopolymer such as polystyrene, poly (α-methylstyrene) and poly (p-methylstyrene), and a styrene-acrylonitrile copolymer ( AS resin), styrene monomer and Maleimide monomers such as reimide and N-phenylmaleimide, and copolymers with acrylamide monomers such as acrylamide, and the like can be given.

  The mixing ratio of carbon black (F) is 0.1 to 5 parts by mass when the total content of components (A) to (H) in the glass fiber reinforced polyamide resin composition of the present invention is 100 parts by mass. Preferably, it is 0.2 to 4.5 parts by mass, more preferably 0.2 to 3.5 parts by mass, and still more preferably 0.2 to 3 parts by mass. If the compounding ratio of the carbon black (F) is less than the above range, the contribution to the weather resistance is reduced, while if it exceeds the above range, the mechanical strength and rigidity tend to be impaired.

  The hindered amine light stabilizer (G) refers to a compound (HALS) having a 2,2,6,6-tetramethylpiperidine structure. HALS is a compound of the following general formula and combinations thereof.

In these formulas, R _{1 to} R ₅ are independent substituents. Examples of suitable substituents are hydrogen, ether, ester, amine, amide, alkyl, alkenyl, alkynyl, aralkyl, cycloalkyl and aryl, where the substituent is then functional. May contain groups. The hindered amine light stabilizer (G) may also form part of a polymer or oligomer.

  Examples of such compounds are: 2,2,6,6-tetramethyl-4-piperidone; 2,2,6,6-tetramethyl-4-piperidinol; bis- (1,2,2,6,6-pentane Methylpiperidyl)-(3 ′, 5′-di-t-butyl-4′-hydroxybenzyl) butylmalonate; di- (2,2,6,6-tetramethyl-4-piperidyl) sebacate (Tinuvin (registered trademark) Oligomers of N- (2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol and succinic acid (Tinuvin® 622); cyanuric acid and N, N Oligomers of di- (2,2,6,6-tetramethyl-4-piperidyl) -hexamethylenediamine; bis- (2,2,6,6-tetramethyl-4-piperidinyl) succine Bis- (1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate (Tinuvin® 123); bis- (1,2,2,6,6-pentamethyl- 4-piperidinyl) sebacate (Tinuvin® 765); Tinuvin® 144; Tinuvin® XT850; tetrakis- (2,2,6,6-tetramethyl-4-piperidyl) -1,2 , 3,4-butanetetracarboxylate; N, N'-bis- (2,2,6,6-tetramethyl-4-piperidyl) -hexane-1,6-diamine (Chimasorb (R) T5); N-butyl-2,2,6,6-tetramethyl-4-piperidinamine; 2,2 ′-[(2,2,6,6-tetramethyl-piperidinium L) -imino] -bis- [ethanol]; poly ((6-morpholine-triazine-2,4-diyl) (2,2,6,6-tetramethyl-4-piperidinyl) -iminohexamethylene- (2 , 2,6,6-tetramethyl-4-piperidinyl) -imino) (Cyasorb (R) UV3346); 5- (2,2,6,6-tetramethyl-4-piperidinyl) -2-cyclo-undecyl -Oxazole) (Hostavin (R) N20); 1,1 '-(1,2-ethane-di-yl) -bis- (3,3', 5,5'-tetramethyl-piperazinone); 8- Acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro (4,5) decane-2,4-dione; polymethylpropyl-3-oxy- [4 (2, 2,6 , 6-Tetramethyl) -piperidinyl] siloxane (Uvasil® 299); 1,2,3,4-butane-tetracarboxylic acid-1,2,3-tris (1,2,2,6,6 -Pentamethyl-4-piperidinyl) -4-tridecyl ester; copolymer of α-methylstyrene-N- (2,2,6,6-tetramethyl-4-piperidinyl) maleimide and N-stearylmaleimide; 3,4-butanetetracarboxylic acid, β, β, β ′, β′-tetramethyl-2,4,8,10-tetraoxaspiro [5.5] undecane-3,9-diethanol, 1,2,2 Polymer with 2,6,6-pentamethyl-4-piperidinyl ester (Mark® LA63); 2,4,8,10-tetraoxaspiro [5.5] undecane-3,9- Β, β, β ′, β′-tetramethyl-polymer with diethanol, 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl-4-piperidinyl ester (Mark ( (Registered trademark) LA68); D-glucitol, 1,3: 2,4-bis-O- (2,2,6,6-tetramethyl-4-piperidinylidene)-(HALS7); 7-oxa- Oligomers of 3,20-diazaspiro [5.1.11.2] -heneicosan-21-one-2,2,4,4-tetramethyl-20- (oxiranylmethyl) (Hostavin® N30); Propanedioic acid, [(4-methoxyphenyl) methylene]-, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) ester (Sanduvor (R) PR31); form Mido, N, N'-1,6-hexanediylbis [N- (2,2,6,6-tetramethyl-4-piperidinyl (Uvinul® 4050H); 1,3,5-triazine-2 , 4,6-triamine, N, N '"-[1,2-ethanediylbis [[[4,6-bis [butyl (1,2,2,6,6-pentamethyl-4-piperidinyl) amino]- 1,3,5-triazin-2-yl] imino] -3,1-propanediyl]]-bis [N ′, N ″ -dibutyl-N ′, N ″ -bis (1,2,2 6,6-pentamethyl-4-piperidinyl) (Chimassorb® 119 MW2286); poly [[6-[(1,1,3,3-tetramethylbutyl) amino] -1,3,5-triazine- 2,4-diyl] [(2,2,6,6 Tetramethyl-4-piperidinyl) -imino] -1,6-hexanediyl [(2,2,6,6-tetramethyl-4-piperidinyl) imino]] (Chimassorb (registered trademark) 944 MW 2000-3000); 1 , 5-Dioxaspiro (5,5) undecane 3,3-dicarboxylic acid, bis (2,2,6,6-tetramethyl-4-peridinyl) ester (Cyasorb® UV-500); Dioxaspiro (5,5) undecane 3,3-dicarboxylic acid, bis (1,2,2,6,6-pentamethyl-4-peridinyl) ester (Cyasorb® UV-516); N-2,2 6,6-tetramethyl-4-piperidinyl-N-amino-oxamide; 4-acryloyloxy-1,2,2,6,6-pentamethyl Le-4-piperidine; 1,5,8,12-tetrakis [2 ′, 4′-bis (1 ″, 2 ″, 2 ″, 6 ″, 6 ″ -pentamethyl-4 ″- Piperidinyl (butyl) amino) -1 ′, 3 ′, 5′-triazin-6′-yl] -1,5,8,12-tetraazadodecane; HALS PB-41 (Clariant Hungingue S.A. A. Nylostab® S-EED (Clariant Hungue SA); 3-Dodecyl-1- (2,2,6,6-tetramethyl-4-piperidyl) -pyrrolidine-2,5-dione; Uvasorb® HA88; 1,1 ′-(1,2-ethane-di-yl) -bis- (3,3 ′, 5,5′-tetra-methyl-piperazinone) (Good-write® 3034); 1,1′1 ″-(1,3,5-triazine-2,4,6-triyltris ((cyclohexylimino) -2,1-ethanediyl) tris (3,3,5,5- Tetramethylpiperazinone) (Good-rite® 3150) and; 1,1 ′, 1 ″-(1,3,5-triazine-2,4,6-triyltris ((cyclohexyl) Silylino) -2,1-ethanediyl) tris (3,3,4,5,5-tetramethylpiperazinone) (Good-lite® 3159);

  The mixing ratio of the hindered amine light stabilizer (G) is 0.05 to 1 when the total content of the components (A) to (H) in the glass fiber reinforced polyamide resin composition of the present invention is 100 parts by mass. 0.0 parts by mass, preferably 0.1 to 1 part by mass. By blending the hindered amine light stabilizer (G) in the above range with the glass fiber reinforced polyamide resin composition of the present invention, the weather resistance is further improved. If the compounding ratio is less than the above range, the contribution to the weather resistance is reduced, while if it exceeds the above range, gas tends to increase during molding and the appearance tends to be impaired.

  As the ultraviolet absorber (H) that can be blended in the present invention, a known ultraviolet absorber can be used. Specifically, 2,2′-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, pt-butylphenyl salicylate, 2,4-di-t-butylphenyl-3, 5-di-t-butyl-4-hydroxybenzoate, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-amyl- Phenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl) phenyl] benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5 ′) -Methylphenyl) -5-chlorobenazotriazole, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) -5-chlorobenzotyriazole 2,5-bis- [5′-t-butylbenzoxazolyl- (2)]-thiophene, bis (3,5-di-t-butyl-4-hydroxybenzylphosphate monoethyl ester) nickel salt, 85-90% of 2-ethoxy-5-t-butyl-2'-ethyloxalic acid-bis-anilide and 2-ethoxy-5-t-butyl-2'-ethyl-4'-t-butyloxalic acid -Bis-anilide 10-15% mixture, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2-ethoxy-2′-ethyloxazaric Acid bisanilide, 2- [2'-hydroxy-5'-methyl-3 '-(3 ", 4", 5 ", 6" -tetrahydrophthalimido-methyl) phenyl] benzotri Azole, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2- (2′-hydroxy-5′-t-octylphenyl) benzotriazole, 2-hydroxy-4-i-octoxybenzophenone, Examples thereof include ultraviolet absorbers such as 2-hydroxy-4-dodecyloxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, and phenyl salicylate. Among these, benzophenone-based, benzotriazole-based, triazole-based, nickel-based, and salicyl-based light stabilizers are preferred, and benzotriazole-based and triazole-based stabilizers are more preferred.

  The compounding ratio of the ultraviolet absorber (H) is 0 to 1.0 mass when the total content of the components (A) to (H) in the glass fiber reinforced polyamide resin composition of the present invention is 100 parts by mass. Parts, preferably 0.1 to 0.8 parts by mass. In the glass fiber reinforced polyamide resin composition of the present invention, the ultraviolet absorber (H) is not an essential component, but when combined with the hindered amine light stabilizer (G) and blended in the above range, the weather resistance is further improved. improves.

  Examples of the copper compound (I) include copper chloride, copper bromide, copper iodide, copper acetate, copper acetylacetonate, copper carbonate, copper borofluoride, copper citrate, copper hydroxide, copper nitrate, copper sulfate, and copper oxalate. And the like. In the glass fiber reinforced polyamide resin composition of the present invention, the content ratio of the copper compound (I) is set to 100 mass of the total content of the components (A) to (H) in the glass fiber reinforced polyamide resin composition of the present invention. Parts, the amount is 0.005 to 1.0 part by mass, preferably 0.01 to 0.5 part by mass. When the content of the copper compound (I) is less than the above range, the heat aging resistance tends to be inferior. On the other hand, when the content exceeds the above range, no further improvement in the heat aging property is observed, and the physical properties deteriorate. Tend to.

  In the present invention, the copper compound (I) may contain an alkali halide compound as a stabilizer in combination with the copper compound. Examples of the alkali halide compound include lithium bromide, lithium iodide, potassium bromide, potassium iodide, sodium bromide, and sodium iodide, with potassium iodide being particularly preferred.

  In addition, the glass fiber reinforced polyamide resin composition of the present invention may further include a fibrous reinforcing material, an inorganic filler, light, or the like in addition to the essential components (A) to (I) as long as the properties of the present invention are not impaired. Optional components such as a phenolic antioxidant, a phosphorus-based antioxidant, a release agent, a crystal nucleating agent, a lubricant, a flame retardant, an antistatic agent, a pigment and a dye can be added as a heat stabilizer. In the glass fiber reinforced polyamide resin composition of the present invention, the total content of optional components other than the essential components (A) to (I) is preferably at most 10% by mass. Further, from the viewpoint of weather resistance, when the total content of the components (A) to (H) of the glass fiber reinforced polyamide resin composition of the present invention is 100 parts by mass, wollastonite is 5 parts by mass or less. It is preferably present, and more preferably not contained.

  The method for producing the glass fiber reinforced polyamide resin composition of the present invention is not particularly limited, and can be obtained by melting and kneading the components by a known kneading method. The specific kneading apparatus is not limited, and examples thereof include a single-screw or twin-screw extruder, a kneader, and a kneader. A twin-screw extruder is particularly preferable in terms of productivity. The screw arrangement is not particularly limited, but it is preferable to provide a kneading zone in order to disperse each component more uniformly. As a specific method, a mixture of a polyamide resin (A), (B), and an acrylic resin (C) is mixed with a hindered amine light stabilizer (G), an ultraviolet absorber (H), a copper compound (I), and others. After pre-blending the components in a blender and feeding them from a hopper to a single-screw or twin-screw extruder, the polyamide resin (A), (B) and the acrylic resin (C) are melted in a molten state. The mica (D) and the glass fiber (E) are charged into a single-screw or twin-screw extruder by a feeder, melt-kneaded, discharged into a strand, cooled, and cut into a mixture.

Since the glass fiber reinforced polyamide resin composition of the present invention is produced with the above-described composition, it is characterized by having the following excellent weather resistance.
That is, the color difference ΔE after a weather resistance test (based on JIS K-7350-2) using a xenon weather meter is 8.0 or less, preferably 7.5 or less, more preferably 7.0 or less. The details of the weather resistance test are in accordance with the procedure described in Examples described later, but a test sample is a mirror-shaped molded product (a flat plate) which is easily affected by the weather resistance evaluation conditions. When the color difference ΔE is equal to or less than the above value, it is possible to withstand outdoor use exposed to rain.

  The effects of the present invention will be specifically shown by the following examples, but the present invention is not limited to the following examples without departing from the technical idea of the present invention. The evaluation of the characteristic values in the examples was performed according to the following method.

(1) Relative viscosity of polyamide resin: 0.25 g of polyamide resin was dissolved in 25 ml of 96% sulfuric acid, 10 ml of this solution was placed in an Ostwald viscometer, measured at 20 ° C., and calculated by the following equation.
RV = T / T0
RV: Relative viscosity, T: Fall time of sample solution, T0: Fall time of solvent

(3) Flexural strength and flexural modulus: Measured according to ISO-178.

(4) Evaluation of weather resistance Color difference ΔE: A mirror flat plate (100 mm × 100 mm × 2 mm) molded at 280 ° C. cylinder temperature and 90 ° C. mold temperature with an injection molding machine (IS80 manufactured by Toshiba Machine Co., Ltd.) Weather test (black panel temperature: 63 ± 2 ° C., relative humidity: 50 ± 5%, irradiation method: 18/120 minutes) in accordance with -7350-2 using a xenon weather meter (XL75 manufactured by Suga Test Instruments Co., Ltd.) Rainfall (water injection), irradiation time: 1250 hours, irradiation intensity: wavelength 300 nm to 400 nm 60 W / m ² · S, optical filter: (inner) quartz, (outer) borosilicate # 275). The L, a, and b values of the mirror flat plate before and after the weather resistance test were measured using a spectrophotometer TC-1500SX manufactured by Tokyo Denshoku Co., Ltd., and the color difference ΔE was calculated.
Surface appearance of molded article after weathering test (with or without exposed reinforcing material):
；: No degree of exposure of the reinforcing material was observed, or a degree of exposure of the reinforcing material was observed on a part of the molded product surface.
×: Exposure of the reinforcing material is observed on the entire surface of the molded article.

・ Polyamide resin (A)
(A1) Polyamide 6 having a relative viscosity RV = 2.0, “M2000” manufactured by MEIDA
(A2) Polyamide 66 having a relative viscosity RV = 2.4, “STABAMID 23AE” manufactured by Rhodia.
・ Amorphous polyamide resin (B)
(B1) Polyamide 6T6I having a relative viscosity RV = 2.0, “Grivory G21” manufactured by EMS,
(B2) Polyamide 6T6I having a relative viscosity RV = 1.8, "Grivory G16" manufactured by Ms.

・ Acrylic resin (C)
Polymethyl methacrylate, Kuraray “Parapet GF”
・ Mica (D)
"S-325" manufactured by Repco
・ Glass fiber (E)
Nippon Electric Glass Co., Ltd. "T-275H" (Circular cross section glass fiber chopped strand: 11 μm in diameter)
・ Carbon black (F)
Masterbatch: Sumika Color Co., Ltd. "EPC-840": Base resin LDPE resin, carbon black content 43% by mass

・ Hindered amine light stabilizer (G)
"Nylostab S-EED" (N, N'-bis- (2,2,6,6-tetramethyl-4-piperidyl) -isophthalamide) manufactured by Clariant.
・ Ultraviolet absorber (H)
“Tinuvin 234” manufactured by BASF (2- [2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl) phenyl] benzotriazole)
・ Copper compound (I)
Cupric bromide: 99.9% purity, manufactured by Wako Pure Chemical Industries, Ltd.

-Other components used Wollastonite: NYGLOS8 manufactured by NYCO MINERAL (fiber diameter 8 µm, fiber length 136 µm)

<Examples 1 to 11, Comparative Examples 1 to 8>
The components other than mica (D), glass fiber (E) and wollastonite are dry-blended at the compounding ratios shown in Tables 1 and 2, and a vented twin-screw extruder “STS35mm” manufactured by Coperion Co., Ltd. (barrel 12 block configuration) ), The mixture was melt-mixed under the extrusion conditions of a cylinder temperature of 280 ° C. and a screw rotation speed of 250 rpm, and then mica (D), glass fiber (E) and wollastonite were supplied by a side feed method and melt-kneaded. The strand extruded from the extruder was quenched and pelletized by a strand cutter. After the obtained pellets were dried at 100 ° C. for 12 hours, a mirror flat plate was formed at a cylinder temperature of 280 ° C. and a mold temperature of 90 ° C. using an injection molding machine (IS80, manufactured by Toshiba Machine Co., Ltd.), and used for evaluation. The evaluation results are also shown in Tables 1 and 2. In addition, the compounding quantity of the carbon black masterbatch (F) in a table | surface is an amount as a masterbatch.

  From Table 1, it can be seen that the test pieces of Examples 1 to 11 have a small color difference ΔE before and after the weathering test, and the black discoloration is suppressed. Further, the exposure of the glass fiber is suppressed, and the surface condition is good. On the other hand, from Table 2, it can be seen that the test piece of Comparative Example 1 containing no hindered amine light stabilizer (G) had a slightly larger color difference ΔE before and after the weather resistance test than the example, and thus had a slightly inferior weather resistance. It can be seen that the test pieces of Comparative Examples 2 to 8 had a large color difference ΔE before and after the weather resistance test, a large fading of black, and impaired appearance. It can be seen that the test pieces of Comparative Examples 6 and 8 are also inferior in flexural strength and flexural modulus.

  The glass fiber reinforced polyamide resin composition of the present invention includes an outer handle, an outer door handle, a wheel cap, a roof rail, a door mirror base, a room mirror arm, a sunroof deflector, a radiator fan, a radiator grill, a bearing retainer, a console box, a sun visor arm, It can be suitably used for interior and exterior parts for vehicles such as spoilers and slide door rail covers.

Claims (5)

  Crystalline aliphatic polyamide resin (A), amorphous polyamide resin (B), acrylic resin (C), mica (D), glass fiber (E), carbon black (F), hindered amine light stabilizer (G) , And the ultraviolet absorber (H) were respectively (10 to 40): (2 to 20): (1 to 10): (2 to 25): (20 to 50): (0.1 to 5): (0 0.05 to 1.0): (0 to 1.0), and when the total content of the components (A) to (H) is 100 parts by mass, the copper compound (I) A glass fiber reinforced polyamide resin composition, which is contained at a ratio of 0.005 to 1.0 part by mass.   The glass fiber reinforced polyamide resin composition according to claim 1, wherein the amorphous polyamide resin (B) is a semi-aromatic polyamide.   The flat plate obtained by injection molding from the glass fiber reinforced polyamide resin composition has a color difference ΔE before and after a weathering test according to JIS-K-7350-2 of 8.0 or less. 3. The glass fiber reinforced polyamide resin composition according to 1 or 2.   A molded article for a vehicle interior or a vehicle exterior, which is molded using the glass fiber reinforced polyamide resin composition according to claim 1. Outer handle, outer door handle, wheel cap, roof rail, door mirror base, room mirror arm, sunroof deflector, radiator fan, radiator grill, bearing retainer, console box, sun visor arm, spoiler, and slide door rail cover The molded article for vehicle interior or vehicle exterior according to claim 4, characterized in that: