JP2017082028A - Glass filament-reinforced polyamide resin composition pellet and method for producing the same and structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a glass filament-reinforced polyamide resin composition that has very high impact resistance, is halogen free, is excellent in flame resistance, has a small dimensional change due to water absorption, is excellent in dimensional stability, and is suitably used in a material such as an electrical component and a vehicle lower part attachment component of an automobile, which requires a welding portion.SOLUTION: There is provided a glass filament-reinforced polyamide resin composition pellet which contains polyamide 610 and/or a polyamide 612 resin (A), a glass fiber (B), an organic phosphorus flame retardant (C), and a lubricant (D). The pellet contains: 30-60 mass% of the glass fiber (B) with respect to 100 mass% of the polyamide resin composition pellet, the glass fiber (B) having a weight average fiber length of 1-15 mm; 10-30 mass% of the organic phosphorus flame retardant (C), the organic phosphorus flame retardant (C) being a melamine phosphate compound and/or a phosphinic acid metal salt compound; and 0.1-1 mass% of the lubricant (D).SELECTED DRAWING: None

Description

  The present invention relates to a long glass fiber reinforced polyamide resin composition pellet, a production method thereof, and a structure.

In general, battery pack cases used in electric vehicles, fuel tanks for automobiles with internal combustion engines, structural reinforcement members that support these, etc. are mounted at the bottom of the vehicle body floor panel, and steel is press-molded. Manufactured or molded using a plastic composite with a steel reinforcement inserted (Patent Document 1).
In addition, the above-mentioned member attached to the lower part of the vehicle body is required to have chipping resistance, airtightness, corrosion resistance, calcium chloride resistance, etc. during actual traveling, and therefore an under cover is separately attached (Patent Document 2). ). Such a mounting structure has a problem of increasing the total weight of the vehicle body and reducing the fuel consumption of the vehicle.

JP 2009-137408 A JP 2005-183217 A

  The purpose of the present invention is to replace the existing lower body mounting structure made of steel or a composite material of steel and plastic with a plastic composite material reinforced with long glass fibers in order to reduce the weight of the automobile. It is to be. That is, the present invention can achieve thinning while achieving high strength and high rigidity, and particularly has a halogen-free and high flame resistance required for battery peripheral members, and has impact resistance and resistance. It is intended to provide a glass long fiber reinforced polyamide resin composition pellet excellent in chemical properties, dimensional stability and weldability, a method for producing the same, and an automobile body lower mounting structure formed by molding the glass long fiber reinforced polyamide resin composition pellet. It is the purpose.

As a result of intensive studies to solve the above problems, the present inventors have found that the present invention can be achieved by blending an appropriate amount of a polyamide resin, a glass fiber having a specific fiber length, a specific organophosphorous flame retardant, and a lubricant. It was completed.
That is, the long glass fiber reinforced polyamide resin composition pellets of the present invention are:
(A) Polyamide 610 and / or polyamide 612 resin, (B) glass fiber, (C) organophosphorus flame retardant, and (D) a long glass fiber reinforced polyamide resin composition pellet containing a lubricant,
For 100% by weight of polyamide resin composition pellets,
(B) 30-60 mass% glass fiber is contained, (B) The weight average fiber length of glass fiber is 1-15 mm,
(C) 10-30% by mass of an organic phosphorus flame retardant, (C) the organic phosphorus flame retardant is a melamine phosphate compound and / or a phosphinic acid metal salt compound,
(D) 0.1-1% by mass of lubricant,
Is included.

It is preferable that the long glass fiber reinforced polyamide resin composition pellets of the present invention further contain 0.1 to 2% by mass of (E) a zinc compound.
It is preferable that the glass long fiber reinforced polyamide resin composition pellet of the present invention further contains 0.1 to 1% by mass of (F) a hindered phenol heat stabilizer and / or a higher fatty acid amide compound.

(A) Polyamide 610 and / or 612 resin preferably has a 98% sulfuric acid relative viscosity ηr (according to JIS K6920) of 2.0 to 3.0.
(B) It is preferable that the number average fiber diameter of glass fiber is 15-20 micrometers.
(D) The lubricant is preferably a higher fatty acid metal salt compound and / or a higher fatty acid ester.

  The manufacturing method of the long glass fiber reinforced polyamide resin composition pellets of the present invention includes (A) polyamide 610 and / or polyamide 612, (B) glass fiber, (C) an organophosphorus flame retardant, and (D) a lubricant. It is preferable to melt-knead a part of the mixture and then extrude to obtain pellets, and then add the remainder of (D) the lubricant to the obtained pellets.

  When the long glass fiber reinforced polyamide resin composition pellets of the present invention further contain (E) a zinc compound, the (E) zinc compound is preferably melt-kneaded together at the time of melt-kneading.

  When the glass long fiber reinforced polyamide resin composition pellets of the present invention further comprise (F) a hindered phenol heat stabilizer and / or a higher fatty acid amide compound, (F) a hindered phenol heat stabilizer and / or a higher fatty acid. The amide compound is preferably melt-kneaded together at the time of melt-kneading.

  The automobile body lower mounting structure of the present invention is formed by molding the long glass fiber reinforced polyamide resin composition pellets of the present invention.

The long glass fiber reinforced polyamide resin composition pellets of the present invention are:
(A) Polyamide 610 and / or polyamide 612 resin, (B) glass fiber, (C) organophosphorus flame retardant, and (D) a long glass fiber reinforced polyamide resin composition pellet containing a lubricant,
For 100% by weight of polyamide resin composition pellets,
(B) 30-60 mass% glass fiber is contained, (B) The weight average fiber length of glass fiber is 1-15 mm,
(C) 10-30% by mass of an organic phosphorus flame retardant, (C) the organic phosphorus flame retardant is a melamine phosphate compound and / or a phosphinic acid metal salt compound,
(D) 0.1-1% by mass of lubricant,
Therefore, for example, a resin that is halogen-free and has high flame resistance, impact resistance, chemical resistance, and excellent dimensional stability and weldability, which is required for a vehicle body lower mounting structure such as a battery pack case. It becomes possible to obtain a pellet made of the composition and a molded product thereof.

The glass long fiber reinforced polyamide resin composition pellets of the present invention (hereinafter also simply referred to as “resin composition pellets” or “pellets”) include (A) polyamide 610 and / or polyamide 612 resin, and (B) glass fibers. And (C) an organophosphorus flame retardant and (D) a long glass fiber reinforced polyamide resin composition pellet containing a lubricant,
For 100% by weight of polyamide resin composition pellets,
(B) 30-60 mass% glass fiber is contained, (B) The weight average fiber length of glass fiber is 1-15 mm,
(C) 10-30% by mass of an organic phosphorus flame retardant, (C) the organic phosphorus flame retardant is a melamine phosphate compound and / or a phosphinic acid metal salt compound,
(D) 0.1-1% by mass of lubricant,
Is included.
Below, each component etc. are demonstrated in detail.

[(A) polyamide 610 and / or polyamide 612 resin (component (A))]
The component (A) polyamide 610 resin is a polyamide resin mainly composed of hexamethylene diamine and sebacic acid, and the polyamide 612 resin is a polyamide resin mainly composed of hexamethylene diamine and dodecanedioic acid. These can be obtained by obtaining commercially available products or by synthesizing them by conventional methods.

 The component (A) preferably has excellent fluidity at the time of molding in order to obtain a thin molded product, and the 25 ° C. and 98% sulfuric acid relative viscosity (ηr) is preferably 2.0 to 3.0, It is more preferably 2.0 to 2.6, and further preferably 2.2 to 2.5. Here, the “relative viscosity” is a 98% sulfuric acid solution containing 1% by mass of a polyamide resin (1% by mass of a mixed resin in the case where the component (A) includes both a polyamide 610 resin and a polyamide 612 resin) It is measured using an Ostwald viscometer according to JIS K6920. By controlling the relative viscosity of the component (A) to be in the above numerical range, a molded product having practically sufficient mechanical properties can be obtained, and the fluidity during molding is good, so that the dimensional stability An excellent molded product can be obtained.

 In the component (A), pigments, colorants, heat stabilizers, light stabilizers, antioxidants, etc., which are contained in ordinary polyamide resins, are added as necessary, as long as the object of the present invention is not impaired. May be. These are used singly or in combination of two or more.

[(B) Glass fiber (component (B))]
The glass fiber of component (B) is preferably a roving having a weight average fiber length of 1 to 15 mm and surface-treated with a sizing agent for polyamide resin. The sizing agent here preferably contains a sizing component for the purpose of sizing and a surface treatment component for the purpose of adhesion between the polyamide resin of component (A).

  The constituent components of the glass fiber sizing agent suitably used in the present invention are not particularly limited. The most preferred sizing agent is mainly composed of a copolymer of maleic anhydride and an unsaturated monomer and a silane coupling agent from the viewpoint of improving mechanical properties.

Specific examples of the copolymer of maleic anhydride and unsaturated monomer constituting the sizing agent (hereinafter also simply referred to as maleic anhydride copolymer) include styrene, α-methylstyrene, butadiene, isoprene, and chloroprene. , Copolymers of unsaturated monomers such as 2,3-dichlorobutadiene, 1,3-pentadiene, cyclooctadiene and maleic anhydride. Among these, a copolymer of butadiene or styrene and maleic anhydride is particularly preferable. Further, two or more of these monomers may be used in combination.
The maleic anhydride copolymer preferably has an average molecular weight of 2,000 or more. Further, the ratio of maleic anhydride and unsaturated monomer is not particularly limited. Furthermore, in addition to the maleic anhydride copolymer, an acrylic acid copolymer or a urethane polymer may be used in combination.

  As the silane coupling agent which is another component constituting the sizing agent, a silane coupling agent usually used for the surface treatment of glass fibers can be used.

Specifically, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) aminopropyltrimethoxysilane, N -Aminosilane coupling agents such as β (aminoethyl) aminopropyltriethoxysilane; γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, etc. Epoxysilane coupling agents: methacryloxy such as γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldiethoxysilane, γ-methacryloxypropyltriethoxysilane Lan-based coupling agent; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (beta-methoxyethoxy) vinylsilane coupling agents such as silane; and the like.
These coupling agents may be used alone or in combination of two or more.
Of these, amino group-containing silane coupling agents are particularly preferred because of their affinity with the polyamide resin of component (A), and among them, γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyl Most preferred is triethoxysilane.

 The ratio of the maleic anhydride copolymer and the silane coupling agent used is preferably a ratio of 0.01 to 20 parts by mass of a silane coupling agent with respect to 100 parts by mass of the maleic anhydride copolymer. Preferably it is 5-20 mass parts, More preferably, it is a ratio of 10-20 mass parts.

  Usually, a maleic anhydride copolymer and a silane coupling agent are mixed in an aqueous solvent and used as a sizing agent. Further, a surfactant, a lubricant, a softening agent, an antistatic agent and the like may be added as necessary.

 The number average fiber diameter of the glass fiber of the component (B) is preferably 15 to 20 μm from the viewpoint of improving mechanical strength. A more preferable range is 15 to 18 μm.

  Moreover, in this invention, the weight average fiber length of (B) component in a pellet is 1-15 mm from a viewpoint of mechanical strength, rigidity, and impact resistance, Preferably it is 5-13 mm, More preferably, it is 8- 12 mm.

 The resin composition pellets of the present invention preferably take the form of long fiber pellets. The long fiber pellet as used in the present invention includes a pellet in which the component (B) is arranged substantially parallel to the longitudinal direction of the pellet and the length of the component (B) in the pellet is equal to or longer than the pellet length. Is. Although arrangement | positioning in a pellet is not specifically limited, It is preferable that it is a pellet formed by arrange | positioning at least (A) component so that the circumference | surroundings of glass fiber may be coat | covered.

 As a means for obtaining such pellets, there is a so-called pultrusion method. Specifically, a glass fiber roving bundle is passed through an impregnation die filled with a molten resin attached to the tip of an extruder, and resin impregnated glass is obtained. The fiber roving bundle is continuously taken out from the spinning nozzle, and the obtained strands are pelletized to a predetermined length to obtain long fiber pellets whose glass fiber length is substantially the same as the pellet length.

 The shape of the resin composition pellets of the present invention is not particularly limited, but from the viewpoint of ease of production, the diameter is preferably 2 mm or more and 5 mm or less from the viewpoint of biting into a molding machine during injection molding. Since the pellet length is also substantially the glass fiber length, the pellet length is preferably 1 mm or more and 15 mm or less, more preferably 5 to 13 mm, and still more preferably 8 to 12 mm. With this pellet length, the fiber length of the component (B) in the molded product when it is formed into an injection molded product can be kept long, so that it is possible to significantly improve impact resistance and improve dimensional stability.

 The weight average fiber length of the component (B) in the molded product obtained by injection molding is preferably 0.3 to 2 mm. The fiber length in the glass fiber reinforcing material pellets compounded by a commercially available, for example, twin screw extruder is only 0.2 to 0.3 mm, and the above-mentioned characteristics are sufficiently developed with this fiber length. It is not possible.

Here, the number average fiber diameter in the present specification is obtained by placing the resin composition pellets in an electric furnace, incinerating the organic matter contained therein, arbitrarily selecting 100 or more glass fibers from the residue, and taking an optical micrograph. And can be determined by measuring the fiber diameter of these glass fibers. Further, the weight average fiber length was measured in the same manner for the above-mentioned 100 or more glass fibers obtained using an optical micrograph at a magnification of 1000 times, and a predetermined calculation formula (N fiber lengths were measured). In this case, weight average fiber length = Σ (i = 1 → N) (fiber length of Nth fiber) ² / Σ (i = 1 → N) (fiber length of Nth fiber)).

 In the resin composition pellet of the present invention, the component (B) is blended in the range of 30 to 60% by mass with respect to 100% by mass of the polyamide resin composition pellet. When it is 30% by mass or more, mechanical strength, rigidity, and impact resistance can be improved, and when it is 60% by mass or less, flame retardancy is exhibited and fluidity is good. Therefore, the thin-wall formability can be improved. Preferably, it is 30-55 mass%, More preferably, it is 35-50 mass%.

[(C) Organophosphorus flame retardant (component (C))]
The organophosphorus flame retardant of component (C) is a melamine phosphate compound and / or a phosphinic acid metal salt compound, specifically one or more selected from the following chemical formula (1) and the following chemical formula (2) It is a mixture of

In the above chemical formula, R ₁ and R ₂ are each independently hydrogen, a linear or branched C ₁ -C ₆ alkyl group, or an aryl group, and R ₃ is a linear or branched C ₁ -C ₁₀ alkylene group. , An arylene group, an alkylarylene group or an arylalkylene group, M is calcium, aluminum, magnesium, strontium, barium or zinc, m is 1 to 4, n is 1 to 4, and x is 1 to 2.

  In the resin composition pellets of the present invention, the component (C) is blended in the range of 10 to 30% by mass with respect to 100% by mass of the polyamide resin composition pellets. When the content is 10% by mass or more, flame retardancy can be improved, and when the content is 30% by mass or less, thin-wall formability, impact resistance, and chemical resistance can be improved.

[(D) Lubricant (component (D))]
Component (D), a lubricant, has the effect of improving moldability such as plasticization and releasability when added to resin composition pellets. Examples include aliphatic carbonization such as paraffin wax and polyolefin wax. Higher fatty acids such as hydrogen, stearic acid and oleic acid, higher aliphatic alcohols such as stearyl alcohol, higher fatty acid metal salts such as aluminum stearate and calcium montanate, higher fatty acid esters such as stearyl stearate and montan wax are used it can. Preferably, sodium salts, lithium salts, calcium salts, magnesium salts of higher fatty acids having 9 or more carbon atoms such as lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, montanic acid, melicic acid, oleic acid, erucic acid, etc. Metal salts such as zinc salts and aluminum salts are more preferably used, such as calcium montanate, sodium montanate, aluminum stearate, calcium stearate, and montanic acid ester. These lubricants may be used alone or in combination of two or more.
The melting point of the lubricant is preferably from 80 to 170 ° C., more preferably from 100 to 150 ° C., and even more preferably from 110 to 140 ° C., from the viewpoint of further improving the appearance and releasability.

 (D) As a method of adding the lubricant, (A) component, (B) component and (C) component are internally added as a raw material component in the step of melt kneading with an extruder, and extruded after melt kneading. There is an external addition to spread on the resin composition pellets. From the viewpoint that the plasticizing effect at the time of extrusion kneading can be expected by internal addition, and that the amount of spread is too large and the lubricant is likely to fall off only by external addition, as described later, (D) It is preferable to add by dividing by addition and external addition.

 In the case of external addition, a known spreading agent that serves to help adhere the lubricant to the resin composition pellets can be used. For example, animal oil such as beef tallow and whale oil, vegetable oil such as rapeseed oil and soybean oil, petroleum-based lubricating oil such as spindle oil and engine oil, dimethyl silicone, pentaerythritol ester, poly (α-olefin), polyethylene glycol, polypropylene glycol, poly Synthetic lubricating oil such as phenyl ether, ionic surfactant such as alkylbenzene sulfonate, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester, Nonionic surfactants such as polyglycerol fatty acid esters, sorbitan fatty acid esters and higher alcohol fatty acid esters, fatty acids such as capric acid and oleic acid, and aliphatic alcohols such as decanol 1,5-pentanediol, polyhydric alcohols, fatty acid esters such as butyl stearate or the like such as glycerin can be used. More preferred are polyethylene glycol and polyoxyethylene sorbitan fatty acid ester. These may be used alone or in combination of two or more.

 Appropriate amounts of these spreading agents are 0.003 to 0.3% by mass with respect to 100% by mass of the polyamide resin composition pellets. If it is this range, generation | occurrence | production of the silver streak to the fallen scattering of a lubricant, blocking by an excessive spreading agent, and a molded article can be suppressed.

 (D) The addition amount of a component is 0.1-1 mass% with respect to 100 mass% of polyamide resin composition pellets, 0.1-0.5 mass% is preferable, 0.1-0.3 mass % Is more preferable. By setting it as 0.1 mass% or more, the improvement effect of plasticization property, mold release property, and weldability is large, and productivity can be improved significantly. Moreover, by setting it as 1 mass% or less, a weldable improvement can be aimed at, generation | occurrence | production of a silver streak can be suppressed, and a favorable molded article external appearance can be obtained.

 The split ratio of internal addition and external addition of the addition amount of these (D) components is not particularly limited, and the molding fluidity, releasability and weldability can be expressed in a well-balanced manner by being dividedly added. The amount of external addition is preferably less than 0.3% by mass, and more preferably 0.2% by mass or less, from the viewpoint of suppressing the falling off of the lubricant and the occurrence of silver streaks on the molded product.

[(E) zinc compound (component (E))]
When the resin composition pellet of the present invention further contains a zinc compound as the component (E), the flame retardancy that is the main object of the present invention can be effectively improved. Although the reason for this is not clear, it is possible to reduce the amount of component (C) while maintaining flame retardancy by using component (E) in combination with component (C), and the thin-wall formability and impact resistance can be reduced. Can be improved.
As the component (E), one or a mixture of two or more selected from zinc oxide, zinc borate, zinc sulfide, zinc stearate, and zinc montanate can be preferably exemplified. The component (E) is preferably blended in an amount of 0.1% by mass or more from the viewpoint of flame retardancy and 2% by mass or less from the viewpoint of impact resistance with respect to 100% by mass of the resin composition pellets. .

[(F) Hindered phenol heat stabilizer and / or higher fatty acid amide compound (component (F))]
When the resin composition pellets of the present invention further contain a hindered phenol heat stabilizer and / or a higher fatty acid amide compound as component (F), they are generated when the resin composition pellets of the present invention are heated or melted. Metal corrosive gas can be suppressed and chemical resistance can be improved.

 The hindered phenol heat stabilizer contains one or more heat stabilizers selected from hindered phenol compounds. A hindered phenol compound is an organic compound containing at least one phenol group, the aromatic part of which is at least one position immediately adjacent to the carbon having the phenolic hydroxyl group as a substituent, preferably both Means an organic compound substituted at the position of The substituent adjacent to the hydroxyl group is an alkyl radical suitably selected from alkyl groups having 1 to 10 carbon atoms, preferably a tertiary butyl group. The molecular weight of the hindered phenol compound is suitably at least about 260, preferably at least about 500, more preferably at least about 600. In particular, it has low volatility at the processing temperature used to form the formulation and is 10% TGA (heat weight loss) of at least 290 ° C, preferably at least 300 ° C, 320 ° C, 340 ° C, most preferably at least 350 ° C. Analysis) Hindered phenols having a weight loss temperature are most preferred.

 Examples of the hindered phenol compound include, but are not limited to, for example, N, N′-hexane-1,6-diylbis [3- (3,5-di-t-butyl-4-hydroxyphenylpropionamide), Pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-) Hydrocinnamamide), triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 3,9-bis {2- [3- (3-t-butyl) -4-hydroxy-5-methylphenyl) propynyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxapyro [5,5] undecane, 3,5-di t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, and 1,3 , 5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanuric acid. These may be used alone or in combination of two or more. Among these, from the viewpoint of improving the heat aging resistance, for example, CIBA Specialty Chemicals, Tarrytown, N .; Y. Tetrakis (methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate)) methane, commercially available as Irganox® 1010 from CIBA Specialty Chemicals as Irganox® 1098 N, N′-hexamethylenebis (3,5-di-t-butyl-hydroxyhydro-cinnamamide), 1,3,5-trimethyl-commercially available from CIBA Specialty Chemicals as Irganox® 1330 2,4,6 Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene is preferred, and Irganox 1098 is most preferred.

 Specific examples of the higher fatty acid amide compound of component (F) include stearic acid amide, oleic acid amide, erucic acid amide, ethylene bisstearyl amide, ethylene bis oleyl amide, N-stearyl stearyl amide, N-stearyl erucamide, and the like. Is mentioned. Preferred are stearic acid amide, erucic acid amide, ethylene bisstearyl amide and N-stearyl erucamide, and more preferred are ethylene bisstearyl amide and N-stearyl erucamide.

 (F) The compounding quantity of a component becomes like this. Preferably it is 0.1-1 mass% with respect to 100 mass% of polyamide resin composition pellets, More preferably, it is 0.3-0.5 mass%. In the above range, the amount of gas generated in the pellet manufacturing process can be reduced.

 In addition, the resin composition pellets of the present invention include a stabilizer such as an ultraviolet absorber, a colorant such as a pigment and a dye, talc, and boron as long as flame resistance, fluidity, impact resistance, and chemical resistance are not reduced. Nucleating agents such as nitride, mineral fillers such as calcium carbonate, wollastonite, kaolin, calcined kaolin and mica, and antistatic agents can also be added.

 The molded product obtained by molding the resin composition pellets of the present invention more preferably has a combustibility in the UL94 standard of 0.8 mm thickness and V-0. In recent years, there is an increasing demand for flame resistance in battery peripheral parts. In particular, the casing and cover parts of devices including devices that can generate heat are preferably V-0 in the UL94 standard.

[Production method of long glass fiber reinforced polyamide resin composition pellets]
The polyamide resin composition pellets of the present invention are obtained by melting and kneading the component (A), the component (B), the component (C), and a part (internal addition) of the component (D) to obtain pellets. It is preferable to produce the pellet by adding the remainder (external addition) of the component (D).

 When the polyamide resin composition pellet of the present invention further contains the component (E), the component (E) is melt-kneaded together at the time of melt-kneading, that is, the component (A), the component (B), and the component (C). And a part of the component (D) are preferably melt-kneaded. Further, when the glass long fiber reinforced polyamide resin composition pellet of the present invention further contains the component (F), the component (F) is melt-kneaded together at the time of melt-kneading, that is, the component (A) and the component (B). It is preferable that the component (C) and a part of the component (D) are melt-kneaded together.

 The method of external addition is not particularly limited, but a known mixing and stirring device can be used. For example, a batch type mixing device such as a tumbler or a Henschel mixer, or a continuous mixing device such as a drum blender can be used. As a method for heating the pellets, a method in which the above-described mixing apparatus is a jacket type and the jacket portion is heated by steam or the like to transfer heat to the pellets is simple and general, but is not limited thereto.

 When using a spreading agent, before adding the component (D), the resin composition pellets and the spreading agent are mixed at a temperature not lower than the melting point of the spreading agent and not higher than the boiling point, so that the spreading agent is mixed on the pellet surface. It is preferable to add and mix the component (D) after forming the film because a uniform coating layer is easily formed.

[Molding]
By molding the polyamide resin composition pellets of the present invention by a method such as injection molding, extrusion molding, compression molding or the like, it is possible to obtain a molded product, for example, an automobile electrical component requiring a welded part or an automobile body lower mounting structure. In particular, the injection molding is particularly suitable in that it can be mass-produced with high dimensional accuracy even for a molded product having a complicated shape such as a molded product having a weld part or a hinge part or an insert molded product, or a thin molded product.

 In injection molding, in order to suppress excessive breakage of the glass fiber, as the molding conditions, the back pressure is lowered, the nozzle diameter is increased, the screw groove depth is increased, and the taper angle is decreased. In addition, it is preferable to lower the compression ratio and to increase the sprue diameter, the runner diameter, and the gate diameter in the molding die. By these measures, the weight average fiber length of the component (B) can be kept long.

  Useful for automobile body lower mounting structures that require high flame resistance, high strength, high rigidity, impact resistance, chemical resistance and thin-wall formability, dimensional stability, and weldability simultaneously as applications of molded products in the present invention In particular, battery pack cases used for electric vehicles are welded by vibration welding, ultrasonic welding, hot plate welding, laser welding, thermal welding, infrared welding, etc. for the upper cover and lower case, structural reinforcement members, etc. In particular, the resin composition pellets of the present invention are particularly useful.

 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In addition, the raw material and measuring method which were used for the Example and the comparative example are shown below.

[raw materials]
(A) Polyamide 610 and / or polyamide 612 resin (a-1): Polyamide 610 (98% sulfuric acid viscosity 2.3)
Percentage of polymerized units consisting of sebacic acid and hexamethylenediamine: 100%
(A-2): Polyamide 612 (98% sulfuric acid viscosity 2.6)
Percentage of polymerized units consisting of dodecanedioic acid and hexamethylenediamine: 100%

(B) Glass fiber (b-1): Glass fiber roving (trade name: ER4301H, manufactured by Chongqing International Composites Co., Ltd., monofilament number average fiber diameter: 17 μm, TEX number: 1200 TEX)
(B-2): Chopped glass fiber (trade name: ECS 03T-275H, manufactured by Nippon Electric Glass, average fiber diameter: 10 μm, average length of chop: 3 mm)

(C) Organophosphorous flame retardant (c-1): Melamine polyphosphate (trade name: PMP-100, manufactured by Nissan Chemical Co., Ltd.)
(C-2): Aluminum diethylphosphinate

(D) Lubricant (d-1): Calcium montanate (trade name: Licomont CaV 102, manufactured by Clariant Japan Co., Ltd.)
(D-2): Aluminum stearate

(E) Zinc compound (e-1): Zinc borate

(F) Hindered phenol-based heat stabilizer and / or higher fatty acid amide compound (f-1): hindered phenol compound (trade name: Irganox 1098, manufactured by CIBA Specialty Chemicals)
(F-2): Ethylenebisstearylamide (EBS, trade name: Kao Wax EB-P, manufactured by Kao Corporation)

[Measuring method]
(1) Flammability Using an injection molding machine (FN-3000, screw diameter 40 mm, manufactured by Nissei Plastic Industry Co., Ltd.), the cylinder temperature is the melting point of polyamide resin + 50 ° C., the mold temperature is 80 ° C., the injection pressure is 65 MPa, A test piece having a length of 125 mm, a width of 13 mm, and a thickness of 0.8 mm was molded from the obtained pellet under molding conditions of an injection time of 5 seconds, a cooling time of 25 seconds, and a screw rotation speed of 200 rpm. The flammability of this test piece was measured according to the method of UL94 standard (standard established by Under Writers Laboratories Inc., USA).

(2) Impact resistance Using an injection molding machine (FN-3000, screw diameter 40 mm, manufactured by Nissei Plastic Industry Co., Ltd.), the cylinder temperature is the melting point of polyamide resin + 50 ° C., the mold temperature is 80 ° C., and the injection pressure is 65 MPa. A multipurpose test piece A type according to ISO 3167 was molded from the obtained pellets under the molding conditions of an injection time of 5 seconds, a cooling time of 25 seconds, and a screw rotation speed of 200 rpm. Further, the multipurpose test piece A was cut into a notched Charpy impact strength test specimen.
Using the obtained notched Charpy impact strength test specimen, according to ISO 179, by Charpy impact strength test equipment (Toyo Seiki Seisakusho: DG-C (A, B) Charpy method) Charpy impact strength was measured.

(3) Water absorption dimensional characteristics Using an injection molding machine (FN-3000, screw diameter 40 mm, manufactured by Nissei Plastic Industry Co., Ltd.), the cylinder temperature is the melting point of polyamide resin + 50 ° C., the mold temperature is 80 ° C., and the injection pressure is 65 MPa. A 100 mm square plate having a thickness of 1 mm was molded from the obtained pellets under molding conditions of an injection time of 5 seconds, a cooling time of 25 seconds, and a screw rotation speed of 200 rpm.
The amount of molding quality immediately after molding and the vertical and horizontal dimensions of 100 mm square were measured, and then the mass and dimensions adjusted to the saturated water absorption state in an atmosphere of 23 ° C. and 50% RH were measured.

(4) Calcium chloride resistance A 50 wt% aqueous solution of calcium chloride was dropped onto the multi-purpose specimen A type obtained in (2) above, and the presence or absence of cracks after standing in a gear oven at 100 ° C for 1 hour was observed. The case of occurrence was judged as C, and the case of no crack occurrence was judged as A.

(5) Weldability The multi-purpose test piece A type obtained in the above (2) was cut so as to be cut at the center portion. The cut surfaces (thickness 4 mm × width 10 mm) of the obtained molded product were welded using a vibration welding machine manufactured by Branson on the conditions of a frequency of 200 Hz and a welding pressure of 30 kN. After applying the crushed stone specified by JIS S5001 to -40 to 50 ° C. under an air pressure of 0.5 MPa and a distance of 350 mm, the welding part is welded by a chipping test apparatus (manufactured by Suga Test Instruments). The crack and crack of the part were confirmed. Based on the weldability of Comparative Example 1 (the chipping resistance performance of the welded portion), it was determined that A was superior, B was equivalent, and C was inferior.

(6) Viscosity of sulfuric acid solution (A) Polyamide 610 and / or polyamide 612 resin was dissolved in 98% sulfuric acid and measured according to JIS K6920.

(7) Weight average fiber length The obtained pellet was heat-ashed at 650 ° C. to take out the fiber. The length was measured while observing a part (500 pieces) of the extracted glass fibers with an optical microscope, and the weight average fiber length was determined.

[Examples 1 and 2, Comparative Examples 1 and 2]
Long glass fiber reinforced polyamide resin composition pellets were produced as follows.
From the top feed port in a twin screw extruder (trade name: ZSK25, manufactured by Coperion), the ratio shown in Table 1 is (a-1) polyamide 610, (c-1) melamine polyphosphate, (c-2) diethyl. Supply aluminum phosphinate, (e-1) zinc borate, (f-1) Irganox 1098, (d-1) calcium montanate, and set the cylinder temperature at the melting point of the polyamide resin + 40 ° C. and the screw rotation speed at 300 rpm. The polyamide resin composition was obtained by kneading.
The obtained polyamide resin composition was supplied to an impregnation die (volume: 375 cc) provided with a resin impregnation roller in a long fiber reinforced resin production apparatus (KOSLFP-212, manufactured by Kobe Steel, Ltd.).

On the other hand, three (b-1) glass fiber rovings were introduced from the roving table into the crosshead of the impregnation die filled with the above-mentioned molten polyamide resin composition at the ratio shown in Table 1. An impregnated glass fiber roving bundle was obtained.
The obtained resin-impregnated glass fiber roving bundle was continuously drawn from the spinning nozzle (diameter 2.2 mm) to obtain one strand. This strand was cooled and solidified in a water-cooled bath. The cooled and solidified strand was made into pellets (length 10 mm, diameter 2.2 mm) with a pelletizer. The weight average fiber length of the glass fiber in this pellet was 10 mm.

[Examples 3 to 6 and Comparative Example 3]
Pellets were obtained in the same procedure as the manufacturing method shown in Example 1 above. Then, Table 1 shows 0.03% by mass of a polyethylene glycol (manufactured by Sanyo Chemical Industries, PEG400) as a spreading agent and (d-1) calcium montanate or (d-2) aluminum stearate in the obtained pellets. Externally added at a ratio and dry blended to obtain long glass fiber reinforced polyamide resin composition pellets.

[Comparative Example 4]
In the production method shown in Example 1 above, pellets were obtained in the same procedure except that (d-1) calcium montanate was not added.

[Comparative Example 5]
A long glass fiber reinforced polyamide resin composition was produced as follows.
L / D (extruder cylinder length / extruder cylinder diameter) having an upstream supply port in the first barrel from the upstream side of the extruder and a downstream supply port in the ninth barrel = 48 (number of barrels: 12) using a twin screw extruder [trade name: ZSK26MC, manufactured by Coperion], melt setting and kneading at a cylinder setting temperature of polyamide resin melting point + 40 ° C. and screw rotation speed of 300 rpm, and polyamide resin composition I got a thing.

  Under such conditions, (a-1) polyamide 610, (c-1) melamine polyphosphate, (c-2) aluminum diethylphosphinate, (e-1) from the upstream supply port at the ratio shown in Table 1. Zinc borate, (f-1) Irganox 1098, (f-2) ethylene bisstearylamide, (d-1) calcium montanate are supplied, and (b-2) chopped glass fiber is supplied from the downstream supply port, These were melt-kneaded, taken out in a strand form from a spinning nozzle (diameter 2.2 mm), and pelletized (3 mm length, 2 mm diameter) with a pelletizer while being cooled and solidified in a water-cooled bath. The weight average fiber length of the glass fiber in this pellet was 0.25 mm.

Thereafter, 0.03 mass% of polyethylene glycol (manufactured by Sanyo Chemical Industries, PEG400) as a spreading agent and (d-2) aluminum stearate are externally added to the obtained pellets in the proportions shown in Table 1, and dry blended. Thus, a long glass fiber reinforced polyamide resin composition pellet was obtained.
The characteristics of the pellets obtained in the examples and comparative examples were evaluated according to the above measurement methods. The evaluation results are shown in Table 1.

The molded articles obtained from any of the pellets of Examples 1 to 6 achieved V-0 in combustibility of 0.8 mm thickness. Moreover, since it was a molded product obtained from long fiber pellets, it had high Charpy impact strength and little dimensional change upon water absorption. At the same time, since it is a molded product made of (A) polyamide 610 or polyamide 612 base and having optimized the addition amount of component (D), it can express calcium chloride resistance and weldability at a high level. all right.
In particular, as to weldability, as shown in Examples 3 to 6, a part of the addition amount of the component (D) necessary for improving the melt fluidity at the time of welding is internally added, and plasticizing property at the time of molding. It has been found that excellent welding performance can be achieved by externally adding the amount necessary for improving the mold releasability, that is, the remainder of the added amount of the component (D).

On the other hand, since the comparative example 1 has few (C) component which is a flame retardant, combustibility was not able to achieve V-0. On the other hand, in Comparative Example 2, since the component (C) was too much, the impact resistance was lowered, and cracks were also observed in the chipping test of the welded portion in the weldability evaluation.
Moreover, since the comparative example 3 has too many (D) components, even if a component (B) is an appropriate quantity, it cannot satisfy combustibility V-0, and a water absorption dimension change, calcium chloride resistance, It was found that the weldability was also adversely affected. As in Comparative Example 4, if the component (D) is not present at all, the melt fluidity at the time of molding is lowered and the molded product is inferior in dimensional stability, and the strength of the welded portion is reduced due to the decrease in melt fluidity at the time of welding. Thus, cracks were observed in the chipping test of the welded part.
In addition, as in Comparative Example 5, the molded product obtained from the pellets that cannot be the long glass fiber pellets of the present invention by using chopped glass fibers is greatly reduced in mechanical properties, particularly impact resistance, and has a water absorption dimension. It turns out that it will be a big change.

  From the above, by using pellets having the composition range of the present invention, the obtained molded product can have high flame resistance, impact resistance, chemical resistance, and moldability, so that it is flame retardant. Therefore, it can be said that it is suitable for an automobile body lower part mounting structure.

Claims (10)

(A) Polyamide 610 and / or polyamide 612 resin, (B) glass fiber, (C) organophosphorus flame retardant, and (D) a long glass fiber reinforced polyamide resin composition pellet containing a lubricant,
For 100 weight percent of the polyamide resin composition pellets,
(B) 30-60 mass% of glass fiber is contained, The weight average fiber length of this (B) glass fiber is 1-15 mm,
10 to 30% by mass of the (C) organophosphorus flame retardant, and the (C) organophosphorus flame retardant is a melamine phosphate compound and / or a phosphinic acid metal salt compound,
0.1 to 1% by mass of the (D) lubricant,
Long glass fiber reinforced polyamide resin composition pellets.   Furthermore, the glass long fiber reinforced polyamide resin composition pellet of Claim 1 which contains 0.1-2 mass% of (E) zinc compounds.   The glass long fiber reinforced polyamide resin composition pellets according to claim 1 or 2, further comprising (F) 0.1 to 1% by mass of a hindered phenol heat stabilizer and / or a higher fatty acid amide compound.   The glass fiber reinforced polyamide resin composition according to claim 1, 2 or 3, wherein the (A) polyamide 610 and / or 612 resin has a 98% sulfuric acid relative viscosity ηr (based on JIS K6920) of 2.0 to 3.0. Pellets.   The number average fiber diameter of said (B) glass fiber is 15-20 micrometers, The glass long fiber reinforced polyamide resin composition pellet of any one of Claims 1-4.   The glass long fiber reinforced polyamide resin composition pellet according to any one of claims 1 to 5, wherein the (D) lubricant is a higher fatty acid metal salt compound and / or a higher fatty acid ester.   It is a manufacturing method of the glass fiber reinforced polyamide resin composition pellet of Claim 1, Comprising: (A) Polyamide 610 and / or polyamide 612, (B) Glass fiber, (C) Organophosphorus flame retardant, (D) A method for producing a long glass fiber reinforced polyamide resin composition pellet, in which a part of the lubricant is melt-kneaded and then extruded to obtain a pellet, and the remainder of the (D) lubricant is added to the pellet.   (E) The manufacturing method of the long glass fiber reinforced polyamide resin composition pellet of Claim 7 which melt-kneads a zinc compound together at the time of the said melt-kneading.   (F) The manufacturing method of the glass long fiber reinforced polyamide resin composition pellet of Claim 7 or 8 which melt-kneads a hindered phenol-type heat stabilizer and / or a higher fatty acid amide compound together at the time of the said melt-kneading.   An automobile body lower mounting structure formed by molding the long glass fiber reinforced polyamide resin composition pellet according to any one of claims 1 to 6.