TWI636868B - Fan molding - Google Patents

Abstract

An object of the present invention is to provide a fan-shaped product that has less deformation of the impeller even if it is operated in a high-temperature environment and in a high-speed rotation state.

The fan molded article of the present invention is characterized by including the following thermoplastic resin composition: The storage elastic modulus E2 'at 110 ° C in the dynamic viscoelasticity measurement of the thermoplastic resin composition is relative to the storage elastic modulus E1' at 85 ° C. The ratio (E2 '/ E1') is 0.90 or more, and the specific storage elastic modulus (E2 '/ ρ) when the storage elastic modulus at 110 ° C is set to E2' and the specific gravity at 23 ° C is set to ρ is Above 4,000MPa.

Description

Fan molding

The present invention relates to a fan molded product. More specifically, the present invention relates to a fan-shaped product that suppresses deformation of an impeller during high-temperature rotation in a high-temperature environment.

Conventionally, polybutylene terephthalate-based resins (PBT-based resins) have been conventionally used as cooling fans for electrical and electronic equipment. However, since PBT resin has a high specific gravity and a large temperature dependence of mechanical strength, there are problems such as an increase in deformation of an impeller when it is operated in a high-temperature environment.

As a fan using a resin other than the PBT resin, a fan including an impeller including a resin composition containing polyphenylene ether and an inorganic filler in a styrene resin has been studied (see Patent Document 1). In addition, a fan in which rod-shaped connecting members are connected to each other to suppress deformation is also studied (see Patent Document 2).

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2000-73992

[Patent Document 2] Japanese Patent Laid-Open No. 2010-236446

However, the invention described in Patent Document 1 is a reusability patent. Because it contains a large amount of polystyrene, it has low heat resistance. When it is operated in a high-temperature environment and high-speed rotation, there is an impeller when the fan rotates. The risk of deformation. In addition, Patent Document 2 The described fan system uses a connecting member to fix the impellers to each other. However, there is a problem such that an effect cannot be obtained with respect to deformation in the circumferential direction due to centrifugal force.

That is, the current situation is that a fan including an impeller that has less deformation even if it is operated in a high-temperature environment and in a high-speed rotation state is unknown.

In view of this, an object of the present invention is to provide a fan-shaped product that has less deformation of the impeller even when it is operated in a high-temperature environment and in a high-speed rotation state.

The present inventors worked hard and found that the above-mentioned problems can be solved by using the following thermoplastic resin composition for a fan-shaped product. The measurement of the storage elastic modulus E2 'at 110 ° C in the dynamic viscoelasticity measurement of the thermoplastic resin composition Storage ratio to storage elastic modulus E1 'at 85 ° C (E2' / E1 '), storage elastic modulus at 110 ° C as E2', and specific gravity at 23 ° C as ρ The modulus of elasticity (E2 '/ ρ) is a specific range.

That is, the present invention is as follows.

[1] A fan-shaped product, comprising a thermoplastic resin composition including a storage elastic modulus E2 ′ at 110 ° C. and a storage elastic modulus E1 at 85 ° C. in a dynamic viscoelasticity measurement of the thermoplastic resin composition. The ratio (E2 '/ E1') is 0.90 or more, and the storage elastic modulus at 110 ° C is set to E2 ', and the specific storage elastic modulus at 23 ° C is set to ρ (E2' / ρ ) Is 4,000 MPa or more.

[2] The fan molded product according to the above [1], wherein the flame retardancy rating (implemented with a test piece thickness of 0.75 mm according to UL94) of the thermoplastic resin composition is V-0.

[3] The fan molded product according to the above [1] or [2], wherein the thermoplastic resin composition is a polyphenylene ether-based resin composition.

[4] The fan molded article according to any one of the above [1] to [3], wherein the thermoplastic resin composition is a polyphenylene ether resin composition: polyphenylene ether (A), styrene resin (B ), And the total mass of the glass fiber (C) is 90% by mass or more, and when the total mass is 100% by mass, 45 to 75% by mass of polyphenylene ether (A) and styrene resin (B) are contained. ~ 5 quality Amount%, glass fiber (C) 25 ~ 50 mass%.

[5] The fan molded article according to any one of the above [1] to [4], wherein the thermoplastic resin composition further contains an organic phosphorus-based flame retardant (D), and the polyphenylene ether (A), styrene When the total mass of the resin (B), glass fiber (C), and organic phosphorus-based flame retardant (D) is 100% by mass, the content of the organic phosphorus-based flame retardant (D) is 5 to 20% by mass.

[6] The fan molded product according to the above [5], wherein when the mass of the organic phosphorus-based flame retardant (D) is 100% by mass, the organic phosphorus-based flame retardant (D) contains a material selected from triphenyl phosphate 70% by mass or more of one or more compounds in the group consisting of ester and phosphazene.

[7] The fan molded article according to any one of the above [1] to [6], wherein the maximum diameter is 200 mm or less.

According to the fan molded product of the present invention, it is possible to provide a fan molded product with less deformation of the impeller and high cooling efficiency even when it is operated in a high-temperature environment and in a high-speed rotation state.

1‧‧‧Fan molding

2‧‧‧DC Brushless Motor

3‧‧‧ aluminum box

4‧‧‧Laser sensor emitter

5‧‧‧ laser sensor receiver

FIG. 1 is a rear view of a fan-shaped product used for evaluation of the amount of deformation of a fan in the example of the present case.

FIG. 2 is a side view of a fan molded product for evaluating the amount of deformation of a fan in the embodiment of the present invention.

FIG. 3 is a cross-sectional view taken along the line A-A in FIG. 1 of a fan molded product for evaluating the amount of deformation of a fan in the embodiment of the present invention.

FIG. 4 is a front view of FIG. 1 of a fan molded product used for evaluating the amount of deformation of a fan in the embodiment of the present invention.

Fig. 5 is a side view of the device for measuring the amount of deformation of a fan in the embodiment of the present case.

Hereinafter, a form for implementing the present invention (hereinafter referred to as "this embodiment") will be described in detail. Explain in detail. The present invention is not limited to the following description, and can be implemented with various changes within the scope of the gist thereof.

The fan molded product of this embodiment includes the following thermoplastic resin composition. The ratio of the storage elastic modulus E2 'at 110 ° C to the storage elastic modulus E1' at 85 ° C in the dynamic viscoelasticity measurement of the thermoplastic resin composition ( E2 '/ E1') is 0.90 or more, and the specific storage elastic modulus (E2 '/ ρ) when the storage elastic modulus at 110 ° C is set to E2' and the specific gravity at 23 ° C is set to ρ is 4,000 MPa. the above.

In addition, in this specification, the storage elastic modulus E1 'at 85 ° C in dynamic viscoelasticity measurement may be simply referred to as "E1'", and the storage elastic modulus E2 'at 110 ° C in dynamic viscoelasticity measurement may be simply referred to as "E1'" "E2 '". In this specification, E1 'and E2' refer to values measured by the method described in "(1) Storage elastic modulus" of the following [Evaluation].

In this specification, the storage elastic modulus (E2 '/ ρ) when the storage elastic modulus at 110 ° C is set to E2' and the specific gravity at 23 ° C is sometimes referred to as "110 ° C Ratio storage elastic modulus "or" E2 '/ ρ ".

[Thermoplastic resin composition]

The ratio (E2 '/ E1') of E2 'to E1' of the said thermoplastic resin composition is 0.90 or more. By setting E2 '/ E1' to 0.90 or more, it is possible to obtain a fan-shaped product having less temperature dependence of the amount of deformation of the impeller due to the ambient temperature during use. The E2 '/ E1' is preferably 0.93 or more, and more preferably 0.95 or more.

The specific storage elastic modulus (E2 '/ ρ) of the thermoplastic resin composition at 110 ° C is 4,000 MPa or more. Here, ρ is a specific gravity measured at 23 ° C in accordance with ISO 1183. By setting the specific storage elastic modulus at 110 ° C to 4,000 MPa or more, it is possible to obtain a fan-shaped product that has a small amount of deformation of the impeller even when it is operated in a high-temperature environment and in a high-speed rotation state. The E2 '/ ρ is preferably 4,200 MPa or more, and more preferably 4,500 MPa or more.

From the viewpoint of obtaining a fan-shaped product with less deformation of the impeller even in a high-temperature environment and a high-speed rotation state, the thermoplastic resin composition described above The specific gravity ρ at 23 ° C is preferably 1.5 or less, and more preferably 1.4 or less.

As a method of controlling E2 '/ E1' and E2 '/ ρ, a method of using a polyphenylene ether-based resin composition as a thermoplastic resin composition for manufacturing a fan molded product is preferred.

The flame retardancy of the thermoplastic resin composition having a thickness of 0.75 mm measured in accordance with UL94 is preferably V-0. Examples of the method for controlling flame retardance include a method using a polyphenylene ether resin composition as the thermoplastic resin composition, a method using a thermoplastic resin composition containing a flame retardant, and the like.

The thermoplastic resin composition is preferably a polyphenylene ether-based resin composition, and more specifically, it preferably contains polyphenylene ether (A), and is optionally selected from a styrene-based resin (B) and glass fiber (C). A polyphenylene ether resin composition of at least one of the group consisting of an organic phosphorus-based flame retardant (D), a polyamide resin (E1), and a polyphenylene sulfide resin (E2).

-Polyphenylene ether (A)-

The polyphenylene ether (A) has a repeating unit of the following general formula (1) and / or (2), and is preferably a homopolymer having a structural unit consisting of the general formula (1) or (2) or containing Copolymers of structural units of general formulae (1) and / or (2).

(In the above general formulae (1) and (2), R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently an alkyl group having 1 to 4 carbon atoms and an aryl group having 6 to 12 carbon atoms 2. Other monovalent radicals are, for example, radicals selected from the group consisting of halogen and hydrogen; except for the cases where R ₅ and R ₆ are both hydrogen)

In addition, as the other monovalent group, hydrogen is preferred. The hydrogen atom of the alkyl group and the aryl group may be substituted with a halogen, a hydroxyl group, or an alkoxy group. Furthermore, the preferred carbon number of the alkyl group is 1 to 3, and the preferred carbon number of the aryl group is 6 to 8.

The number of repeating units in the general formulae (1) and (2) can be set to various numbers according to the molecular weight distribution of the polyphenylene ether (A), and is not particularly limited.

Among the polyphenylene ethers (A), the homopolymer is not limited to the following, and examples thereof include poly (2,6-dimethyl-1,4-phenylene) ether and poly (2-methyl -6-ethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2-ethyl-6-n-propyl-1) , 4-phenylene) ether, poly (2,6-di-n-propyl-1,4-phenylene) ether, poly (2-methyl-6-n-butyl-1,4-phenylene) ) Ether, poly (2-ethyl-6-isopropyl-1,4-phenylene) ether, poly (2-methyl-6-chloroethyl-1,4-phenylene) ether, poly (2-methyl-6-hydroxyethyl-1,4-phenylene) ether, and poly (2-methyl-6-chloroethyl-1,4-phenylene) ether, especially for raw materials From the viewpoints of availability and processability, poly (2,6-dimethyl-1,4-phenylene) ether is preferred.

Among the polyphenylene ethers (A), the copolymer is not limited to the following, and examples thereof include a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, and 2,6- Copolymers of dimethylphenol and ortho-cresol, and copolymers of 2,3,6-trimethylphenol and ortho-cresol, which are based on polyphenylene ether structures, especially the ease of obtaining raw materials and processability From the viewpoint, a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol is preferable, and from the viewpoint of improving physical properties, 2,6-dimethylphenol is more preferable. Copolymer with 2,3,6-trimethylphenol (especially containing 90-70% by mass of 2,6-dimethylphenol portion and 10-30% by mass of 2,3,6-trimethylphenol portion Copolymers).

The various polyphenylene ethers (A) described above may be used alone or in combination of two or more.

As long as the heat resistance of the thermoplastic resin composition is not excessively reduced, the polyphenylene ether (A) may contain a polyphenylene ether unit other than the general formulae (1) and (2) as a partial structure. Phenyl ether. Such a phenylene ether unit is not limited to the following examples. For example: 2- (dialkylaminomethyl) -6-methylphenylene ether derived from Japanese Patent Laid-Open No. 01-297428 and Japanese Patent Laid-Open No. 63-301222 Units, or units derived from 2- (N-alkyl-N-phenylaminomethyl) -6-methylphenylene ether.

The polyphenylene ether (A) may also be bonded to a unit derived from biphenylquinone in the main chain of the polyphenylene ether.

Further, the polyphenylene ether (A) may be selected from a group consisting of a part or all of the polyphenylene ether and a functional group containing a fluorenyl group, and selected from the group consisting of a carboxylic acid, an anhydride, a fluorene imine, an amine, an orthoester, a hydroxyl group, and a carboxylic acid. The functionalizing agent of one or more functional groups in the group composed of the ammonium acid salt reacts (modifies) and has a structure substituted with a functionalized polyphenylene ether.

From the viewpoint of the moldability of the thermoplastic resin composition, the ratio (Mw / Mn value) of the weight average molecular weight Mw to the number average molecular weight Mn (Mw / Mn value) of the polyphenylene ether (A) is preferably 2.0 or more, and more preferably 2.5 or more. Furthermore, it is more preferably 3.0 or more, and from the viewpoint of the mechanical properties of the thermoplastic resin composition, it is preferably 5.5 or less, and more preferably 4.5 or less.

The weight-average molecular weight Mw and the number-average molecular weight Mn can be obtained by measuring the obtained polystyrene-equivalent molecular weight by GPC (Gel Permeation Chromatography).

From the viewpoint of sufficient mechanical properties, the specific viscosity of the polyphenylene ether (A) is preferably 0.25 dl / g or more, more preferably 0.30 dl / g or more, and still more preferably 0.33 dl / g or more. From the viewpoint of molding processability, it is preferably 0.65 dl / g or less, more preferably 0.55 dl / g or less, and even more preferably 0.42 dl / g or less.

In addition, the reduced viscosity can be measured using a black viscometer using a chloroform solvent at a solution of 30 ° C and 0.5 g / dl.

When the total mass of the polyphenylene ether (A), the styrene resin (B), and the glass fiber (C) is 100% by mass, the content of the polyphenylene ether (A) is preferably 20% by mass or more, and more preferably It is 25 mass% or more, more preferably 45 mass% or more, and even more preferably 55 mass% or more. The content is preferably 75% by mass or less, more preferably 70% by mass or less, and even more preferably 65% by mass or more. under. When the content of the polyphenylene ether (A) is 45% by mass or more, the effect of imparting heat resistance and flame retardancy is exhibited. From the viewpoint of molding processability, 75% by mass or less is preferable.

From the viewpoint of imparting sufficient heat resistance and flame retardancy, the total mass of polyphenylene ether (A), styrene resin (B), glass fiber (C), and organic phosphorus flame retardant (D) is 100 mass In%, the content of polyphenylene ether (A) is preferably 25% by mass or more, more preferably 35% by mass or more, and still more preferably 40% by mass or more. From the viewpoint of molding processability, it is more preferably 75 mass% or less, more preferably 60 mass% or less, and still more preferably 55 mass% or less.

-Styrenic resin (B)-

From the viewpoint of improving molding fluidity, the thermoplastic resin composition may include a styrene resin (B).

In the thermoplastic resin composition, the styrene-based resin (B) is a polymer obtained by polymerizing a styrene-based compound in the presence or absence of a rubbery polymer, or a styrene-based compound A copolymer obtained by copolymerizing a compound in which an ethylene-based compound is copolymerized in the presence or absence of a rubbery polymer.

The styrene-based compound refers to a compound in which one or more hydrogen atoms of styrene are substituted with a monovalent group.

The styrene-based compound is not limited to the following, and examples thereof include styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, p-methylstyrene, and Tributylstyrene, ethylstyrene, and the like are particularly preferably styrene from the viewpoint of the balance between the availability of stable raw materials and the characteristics of the composition.

The compound that can be copolymerized with the styrene-based compound is not limited to the following, and examples thereof include methacrylates such as methyl methacrylate and ethyl methacrylate; acrylonitrile, methacrylonitrile, and the like Saturated nitrile compounds; unsaturated anhydrides such as maleic anhydride.

Furthermore, the polymer or copolymer obtained by polymerizing or copolymerizing in the presence of a rubbery polymer among the above-mentioned styrene-based resins is referred to as "rubber-reinforced styrene-based "Resin", a polymer or copolymer obtained by polymerizing or copolymerizing in the absence of a rubbery polymer is called "a styrene-based resin that is not rubber-reinforced."

The styrene-based resin (B) is preferably a styrene-based resin that is not reinforced with rubber from the viewpoint of the mechanical properties of the fan molded product.

When the total mass of the polyphenylene ether (A), the styrene resin (B), and the glass fiber (C) is 100% by mass, the content of the styrene resin (B) is preferably 5% by mass or less, more preferably It is preferably 3% by mass or less, and even more preferably it does not substantially contain a styrene resin (B). When the content of the styrene-based resin (B) is 5% by mass or less, heat resistance and flame retardance are excellent, so it is preferable.

From the viewpoint of providing sufficient heat resistance and flame retardancy, the total mass of the polyphenylene ether (A), the styrene resin (B), the glass fiber (C), and the organic phosphorus flame retardant (D) is 100 The content of the styrene-based resin (B) in the mass% is preferably 5 mass% or less, and more preferably 3 mass% or less.

-Glass fiber (C)-

It is preferable that the said thermoplastic resin composition contains glass fiber (C). In the said thermoplastic resin composition, glass fiber (C) is mix | blended in order to improve mechanical strength.

As the kind of glass of the glass fiber (C), a known one can be used, and examples thereof include E glass, C glass, S glass, and A glass. Glass fiber (C) refers to fiber-shaped glass, which is different from lumpy glass flakes or glass powder.

The average fiber diameter of the glass fiber (C) is preferably from the viewpoint of reduction in rigidity, heat resistance, impact resistance, durability, etc. of the molded body due to fiber breakage during extrusion or molding, or production stability. It is 5 μm or more, more preferably 7 μm or more, and from the viewpoint of providing sufficient mechanical physical properties or maintaining the surface appearance of the molded body, it is preferably 15 μm or less, and more preferably 13 μm or less.

From the viewpoint of operability, the average length of the glass fiber (C) is preferably 0.5 mm or more, more preferably 1 mm or more, still more preferably 10 mm or less, and even more preferably 6 mm or less.

From the viewpoint of the balance between rigidity, durability, molding processability, and molding appearance, the average L / D ratio (ratio of the length to the fiber diameter) of the glass fiber (C) is preferably 70 or more, and more preferably 100. The above is preferably 200 or more, more preferably 1200 or less, more preferably 1000 or less, and most preferably 800 or less.

The glass fiber (C) may be a surface treated with a surface treatment agent such as a silane compound. Silane compounds used for surface treatment are generally used when surface treating glass fillers or mineral fillers. Specific examples of the silane compound include vinyl silane compounds such as vinyltrichlorosilane, vinyltriethoxysilane, and γ-methacryloxypropyltrimethoxysilane; γ-shrinkage Glyceryloxypropyltrimethoxysilane and other epoxy silane compounds; bis (3-triethoxysilylpropyl) tetrasulfide and other sulfur-based silane compounds; γ-mercaptopropyltrimethoxysilyl and the like Mercaptosilane compounds; aminosilane compounds such as γ-aminopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, etc. are particularly preferred from the viewpoint of achieving the purpose of the present invention. Aminosilane compounds. These silane compounds may be used alone or in combination of two or more. Further, these silane compounds may be mixed with an epoxy-based or urethane-based sizing agent in advance, and the mixture may be used for surface treatment.

When the total mass of the polyphenylene ether (A), the styrene resin (B), and the glass fiber (C) is 100% by mass, the content of the glass fiber (C) is preferably 20% by mass or more, more preferably 25 mass% or more, more preferably 30 mass% or more, more preferably 80 mass% or less, more preferably 50 mass% or less, still more preferably 45 mass% or less, and even more preferably 40 mass% or less. When the content of the glass fiber (C) is 20% by mass or more, the effect of increasing the mechanical strength of the thermoplastic resin composition and suppressing the deformation of the impeller is exerted. When it is 50% by mass or less, the flame retardance of the thermoplastic resin composition can be improved. It's better.

From the viewpoint of improving the mechanical properties of the thermoplastic resin composition, the total mass of the polyphenylene ether (A), styrene-based resin (B), glass fiber (C), and organic phosphorus-based flame retardant (D) is 100% by mass In the glass fiber (C), the content is preferably 20% by mass or more, and more preferably 30% by mass Above, from the viewpoint of imparting flame retardancy to the thermoplastic resin composition, it is preferably 80% by mass or less, more preferably 50% by mass or less, and still more preferably 45% by mass or less.

-Organic phosphorus flame retardant (D)-

The thermoplastic resin composition preferably further contains an organic phosphorus-based flame retardant (D). Here, the organic phosphorus-based flame retardant refers to a flame retardant including an organic compound containing phosphorus, a flame retardant including an inorganic compound containing phosphorus, and a flame retardant including an organic phosphoric acid and a salt of a metal are not included therein.

As the organic phosphorus-based flame retardant (D), specifically, one or more compounds selected from the group consisting of triphenyl phosphate and phosphazene are preferred. Furthermore, when the mass of the organic phosphorus-based flame retardant (D) is 100% by mass, it is preferable that 70% by mass or more of one or more compounds selected from the group consisting of triphenyl phosphate and phosphazene be contained. Thereby, the effects of imparting flame retardance and maintaining heat resistance are exerted. Especially from the viewpoint that the effect of the present invention can be easily obtained, phosphazene is preferred.

When using triphenyl phosphate alone as the organic phosphorus-based flame retardant (D), from the viewpoint of sufficiently obtaining the effects of the present invention, polyphenylene ether (A), styrene resin (B), glass The content of triphenyl phosphate in 100 mass% of the total mass of the fiber (C) and the organic phosphorus-based flame retardant (D) is preferably 5 mass% or more. It is preferably 13% by mass or less, and more preferably 10% by mass or less from the viewpoint of improving heat resistance.

Examples of the phosphazene include those containing a structural unit represented by the following general formula (3).

(In the general formula (3), X represents Ph (phenyl) or OPh (phenoxy))

The phosphazene is not limited as long as it contains a structural unit represented by the general formula (3), and examples thereof include a cyclic phosphazene compound, a chain phosphazene compound, and a crosslinking crosslinked with a crosslinking group. Phosphazene compounds and the like.

In the thermoplastic resin composition, as the phosphazene, a cyclic phosphazene compound is preferable, and a cyclic phenoxyphosphazene compound is more preferable from the viewpoint of imparting better flame retardancy. In addition, as the phosphazene, from the viewpoint of moldability and flame retardancy, a cyclic phenoxyphosphazene compound containing a terpolymer of 70% by mass or more, and more preferably 85% by mass or more is preferable.

When phosphazene is used alone as the organic phosphorus-based flame retardant (D), polyphenylene ether (A), styrene-based resin (B), glass fiber (C), and organic phosphorus-based flame retardant (D) In the total mass of 100% by mass, the content of phosphazene is not particularly limited as long as it is 5 to 20% by mass.

The organic phosphorus-based flame retardant (D) may be a compound other than triphenyl phosphate and phosphazene in an amount of less than 30% by mass, and may be, for example, an aromatic phosphate other than triphenyl phosphate.

The aromatic phosphate is not limited to the following. For example, triphenyl phosphate, tricresyl phosphate, tris (xylyl) phosphate, cresyl phosphate diphenyl, and (xylyl) phosphate are preferred. Triphenyl substituted aromatic phosphoric acid such as diphenyl ester, bis (xylyl) phosphate, hydroxynon bisphenol phosphate, resorcinol bisphosphate, bisphenol A bisphosphate, etc. Among the esters, triphenyl phosphate is more preferred.

In the case where a mixture of an aromatic phosphate and phosphazene is used as the organic phosphorus-based flame retardant (D), from the viewpoint of imparting better mold flowability and mechanical properties, the thermoplastic resin composition described above is preferred. It is used in a combination ratio of aromatic phosphate and phosphazene (aromatic phosphate: phosphazene) of 5: 95 ~ 30: 70, more preferably in a combination ratio of 10: 90 ~ 25: 75 It is more preferable to use it at a combined ratio of 20:80 to 25:75.

From the viewpoint of flame retardancy, when the total mass of the polyphenylene ether (A), the styrene resin (B), the glass fiber (C), and the organic phosphorus flame retardant (D) is 100% by mass, The content of the organic phosphorus-based flame retardant (D) is preferably 5% by mass or more. From the viewpoint of heat resistance, it is preferably 20% by mass or less, more preferably 13% by mass or less, and even more preferably 10% by mass or less.

-Polyamine resin (E1)-

The polyamide resin (E1) is not particularly limited as long as it has an amino bond -NH-C (= O)-in a repeating unit of the polymer main chain. Polyamide resins can generally be obtained by polycondensation of diamines and dicarboxylic acids, ring-opening polymerization of lactams, polycondensation of aminocarboxylic acids, and the like. The production method of polyamine resins is not limited to this. Other methods may also be polyamide resins obtained by other methods.

Examples of the diamine include an aliphatic diamine, an alicyclic diamine, and an aromatic diamine. Specific examples of the diamine include, for example, tetramethylenediamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, tridecethylenediamine, 2, 2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, 1,9-nonanediamine, 2 -Methyl-1,8-octanediamine, ethylenediamine, propylenediamine, 1,4-butanediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,10-decane Amine, 1,12-dodecanediamine, 3-methyl-1,5-pentanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-triamine Aliphatic diamines such as methyl-1,6-hexanediamine, 5-methyl-1,9-nonanediamine; 1,3-bisaminomethylcyclohexane, 1,4-bisaminomethyl Alicyclic diamines such as cyclohexane; aromatic diamines such as m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, and p-xylylenediamine.

Examples of the dicarboxylic acid include an aliphatic dicarboxylic acid, an alicyclic dicarboxylic acid, and an aromatic dicarboxylic acid. Specific examples of the dicarboxylic acid include malonic acid, dimethylmalonic acid, succinic acid, 3,3-diethylsuccinic acid, glutaric acid, and 2,2-dimethylpentane. Aliphatic dicarboxylic acids such as diacid, adipic acid, 2-methyladipic acid, trimethyladipic acid, suberic acid, pimelic acid, azelaic acid, sebacic acid, dodecanedioic acid; Alicyclic dicarboxylic acids such as 1,1,3-tridecanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid Acid; terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, such as naphthalenedicarboxylic acid, dimer acid, 1, 4-phenylene dioxydiacetic acid, 1,3-phenylene dioxydiacetic acid, diphthalic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylfluorene-4,4 Aromatic dicarboxylic acids such as' -dicarboxylic acid and 4,4'-biphenyldicarboxylic acid, and the like. These may be used individually by 1 type, and may use 2 or more types together.

Examples of the lactams include ε-caprolactam, ω-heptalactam, ω-laurolactam, and the like.

Examples of the aminocarboxylic acid include ε-aminohexanoic acid, 7-aminoheptanoic acid, 8-aminocaprylic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, and 12-aminodeca Diacid, 13-aminotridecanoic acid, etc.

A diamine, a dicarboxylic acid, a lactam, and an aminocarboxylic acid may be used individually by 1 type, and may use 2 or more types together. It is also possible to use a stage in which a diamine, a dicarboxylic acid, a lactam, and an amine carboxylic acid are polymerized to a low molecular weight oligomer in a polymerization reactor, and the molecular weight is increased in an extruder, etc. Into a person.

Examples of the polyamide resin (E1) include polyamide 6, polyamide 6,6, polyamide 4,6, polyamide 11, polyamide 12, polyamide 6,10, Polyamine 6,12, Polyamide 6 / 6,6, Polyamine 6 / 6,12, Polyamide MXD (m-xylenediamine, m-xylenediamine), 6, Polyamine 6, T, Polyamide 9, T, Polyamide 6, I, Polyamide 6/6, T, Polyamide 6/6, I, Polyamide 6,6 / 6, T, Polyamide 6,6 / 6, I, polyamide 6/6, T / 6, I, polyamide 6,6 / 6, T / 6, I, polyamide 6/12/6, T, polyamide 6,6 / 12/6, T, polyamide 6/12/6, I, polyamide 6,6 / 12/6, I, polyamide 9, T, etc. These may be used individually by 1 type, and may use 2 or more types together.

From the viewpoints of heat resistance and dimensional stability at the time of water absorption of the molded product, the polyamide resin (E1) preferably contains a semi-aromatic polyamide. The semi-aromatic polyamine is a polymer containing (a) a dicarboxylic acid unit and (b) a diamine unit, and at least a part of either of (a) the dicarboxylic acid unit and (b) the diamine unit is aromatic Family of compounds. As the semi-aromatic polyamine, it is preferable to use the semi-aromatic polyamine described in detail below.

From the viewpoints of flame retardancy and heat resistance, the semi-aromatic polyamine preferably contains a terephthalic acid unit as the (a) dicarboxylic acid unit. (a) The content of the terephthalic acid unit in the dicarboxylic acid unit is preferably 60 to 100 mol%, more preferably 75 to 100 mol%, even more preferably 90 to 100 mol%, and even more preferably Substantially all dicarboxylic acid units (a) are terephthalic acid unit.

The content of the dicarboxylic acid units other than the terephthalic acid unit in the (a) dicarboxylic acid unit of the semi-aromatic polyamine is preferably less than 40 mol%, more preferably less than 25 mol%, It is more preferably less than 10 mol%, and still more preferably does not substantially contain other dicarboxylic acid units.

Examples of the dicarboxylic acid unit other than the terephthalic acid unit include units derived from the above-mentioned dicarboxylic acid other than the terephthalic acid. These may be used individually by 1 type, and may use 2 or more types together. Units derived from an aromatic dicarboxylic acid other than terephthalic acid are particularly preferred. Furthermore, the unit derived from a trivalent or higher polyvalent carboxylic acid such as trimellitic acid, pyromellitic acid, pyromellitic acid and the like may be contained within a range capable of being melt-molded.

From the viewpoint of dimensional stability when absorbing water in the fan-molded product of the present embodiment, the semi-aromatic polyamidoamine preferably contains (b-1) 1,9-nonanediamine unit and / or (b- 2) A 2-methyl-1,8-octanediamine unit is used as (b) a diamine unit.

(b) The total content of (b-1) 1,9-nonanediamine unit and (b-2) 2-methyl-1,8-octanediamine unit in the diamine unit is preferably 60 to 100 moles. Ear%, more preferably 75 to 100 mole%, more preferably 90 to 100 mole%, and even more preferably substantially all of the diamine units are composed of (b-1) 1,9-nonanediamine units and / Or (b-2) 2-methyl-1,8-octanediamine unit.

The content of (b) diamine units in the semi-aromatic polyamines is preferably 1,9-nonanediamine units and other diamine units other than 2-methyl-1,8-octanediamine units. It is 40 mol%, more preferably 25 mol%, more preferably 10 mol%, and even more preferably, it does not substantially contain other diamine units.

Examples of the diamine unit other than the 1,9-nonanediamine unit and the 2-methyl-1,8-octanediamine unit include units derived from the following components: ethylenediamine, propylenediamine, 1 1,4-butanediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,10-decanediamine, 1,12-dodecanediamine, 3-methyl-1,5- Pentylenediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 5-methyl-1,9-nonan Aliphatic diamines such as diamines; alicyclic diamines such as cyclohexanediamine, methylcyclohexanediamine, isophoronediamine; p-phenylenediamine, m-phenylenediamine, xylylenediamine, 4, 4'-two Aromatic diamines such as aminodiphenylmethane, 4,4'-diaminodiphenylphosphonium, and 4,4'-diaminodiphenyl ether. These may be used individually by 1 type, and may use 2 or more types together.

(B-1) 1,9-nonanediamine unit and (b-2) 2-methyl-1,8-octanediamine unit among (b) diamine units contained in the semi-aromatic polyamine When the total amount is 100 mol%, the content of (b-1) 1,9-nonanediamine unit is preferably 60 mol% or more, more preferably 75 mol% or more, and even more preferably 80 mol%. Ear%. When the content of the (b-1) unit is within the above range, the heat resistance is further improved, and the water absorption of the molded product can be further effectively suppressed. When the total amount of the (b-1) unit and the (b-2) unit in the (b) diamine unit is 100 mol%, the content of the (b-1) unit is preferably 95 mol% or less, It is more preferably 90 mol% or less, and still more preferably 85 mol% or less. When the content of the (b-1) unit is within the above range, mechanical properties such as impact resistance and stretching are further improved, and the surface appearance of the fan molded product can be made more excellent.

As the polyamide-based resin (E1), a polyamide-based resin obtained by copolymerizing a plurality of polyamide-based resins by an extruder or the like can also be used.

The viscosity value of the polyamide resin (E1) (viscosity value measured using 96% sulfuric acid according to ISO 307: 1994) is preferably 50 mL / g or more, more preferably 70 mL / g or more, and even more preferably 100 mL / g the above. Moreover, it is preferably 250 mL / g or less, more preferably 200 mL / g or less, and still more preferably 150 mL / g or less.

By setting the viscosity value of the polyamide resin (E1) to 50 mL / g or more, the flame retardancy and the processability such as extrusion are further improved, and the generation of gas during molding is further suppressed. In addition, by setting the viscosity value to 50 mL / g or more, the occurrence of mold deposits can be reduced, and the number of injections that can be normally molded during injection molding can be dramatically increased, thereby greatly improving moldability. In addition, by setting the viscosity value to 250 mL / g or less, in addition to the effects described above, effects such as improving the moldability of a thin-walled molded product can also be obtained.

It is desirable to obtain a more excellent effect by using a polyamide resin in the range of the above-mentioned viscosity value. When a further excellent effect is desired, it is more preferable to be as follows according to the type of the polyamide resin. The manner of the viscosity value is controlled.

For example, from the viewpoint of the balance between toughness and molding fluidity, semi-aromatic polyamides such as polyamide 9, T or polyamide 6,6 / 6, I are used as the polyamide resin (E1). Compared with the case where a semi-aromatic polyamide is not used as the polyamide resin, the preferable viscosity range is slightly different. In the case of polyamide 9, T, the preferred range of the viscosity value is preferably 70 mL / g or more, and more preferably 100 mL / g or more. The viscosity value is preferably 150 mL / g or less, and more preferably 120 mL / g or less.

In the case of polyamide 6,6 / 6, I, the viscosity value is preferably 50 mL / g or more, and more preferably 70 mL / g or more. The viscosity value is preferably 150 mL / g or less, more preferably 130 mL / g or less, and even more preferably 120 mL / g or less.

The inventors have found that when a polyamide resin (E1) is used in the thermoplastic resin composition, the balance between the moldability and impact resistance of the thermoplastic resin composition is affected by the viscosity of the polyamide resin (E1) The effect of the value is large. From such a viewpoint, by using a polyamide-based resin having the above-mentioned viscosity value, an improvement in particular characteristics can be observed.

The polyamide resin (E1) may also be a mixture of a plurality of polyamide resins having different viscosity values. The viscosity value of the polyamide resin (E1) in the thermoplastic resin composition can be confirmed by the following method.

First, the resin portion of the thermoplastic resin composition is dissolved with 1,1,1,3,3,3-hexafluoro-2-propanol, and then the resin portion contained in the soluble portion is precipitated and separated using methanol. After further dissolving the fraction with formic acid or sulfuric acid, the soluble fraction is fractionated using a centrifuge or the like. This soluble portion was reprecipitated with methanol, and the polyamide resin component was fractionated, and the viscosity value was then measured to confirm it.

From the viewpoint of the dimensional stability of the molded product when it absorbs water or the surface appearance of the molded product, it is particularly preferred that the polyamide resin (E1) contains 70 to 95% by mass of hexamethylene dihexamethylene diamine unit, and Semi-aromatic polyamidine having 5 to 30% by mass of methylene m-xylylenediamine unit. Furthermore, adipic acid hexanediamine can be obtained from, for example, adipic acid and hexanediamine. Hexamethylene m-xylylenediamine can be obtained, for example, from isophthalic acid and hexamethylene diamine.

The terminal group of the polyamide resin (E1) participates in the reaction with the polyphenylene ether (A). Generally, a polyamido resin has an amine group or a carboxyl group as a terminal group. Generally, as the terminal carboxyl group concentration becomes higher, the impact resistance tends to decrease and the fluidity tends to improve.

From the viewpoint of further optimizing the characteristic balance of the thermoplastic resin composition, the ratio (mole) of the terminal amine group concentration to the terminal carboxyl group concentration of the polyamide resin (E1) is preferably 1.0 or less, and more preferably 0.05. ~ 0.8. By setting the ratio of the terminal amine group concentration to the terminal carboxyl group concentration of the polyamide resin (E1) within the above range, the balance between the fluidity and impact resistance of the thermoplastic resin composition can be maintained at a higher level .

The terminal amine group concentration of the polyamide resin (E1) is preferably 1 μmol or more, more preferably 5 μmol / g or more, still more preferably 10 μmol / g or more, and even more preferably 20 μmol / g or more. It is preferably 80 μmol / g or less, more preferably 60 μmol / g or less, even more preferably 45 μmol / g or less, and even more preferably 40 μmol / g or less. By setting the terminal amine group concentration within the above range, the balance between the fluidity and impact resistance of the thermoplastic resin composition can be maintained at a higher level.

The terminal carboxyl group concentration of the polyamide resin (E1) is preferably 20 μmol / g or more, and more preferably 30 μmol / g or more. It is preferably 150 μmol / g or less, and more preferably 130 μmol / g or less. By setting the terminal carboxyl group concentration within the above range, the balance between the fluidity and impact resistance of the thermoplastic resin composition can be maintained at a higher level.

The concentration of each terminal group of these polyamide-based resins can be adjusted by a known method. For example, a method of adding one or more selected from the group consisting of a diamine compound, a monoamine compound, a dicarboxylic acid compound, and a monocarboxylic acid compound so as to have a specific terminal group concentration during the polymerization of the polyamine resin. Wait.

The terminal amine group concentration and the terminal carboxyl group concentration can be measured by various methods. For example, from the viewpoints of accuracy and simplicity, a method of obtaining the integral value of the characteristic signal corresponding to each terminal group by ¹ H-NMR is preferable. For example, as a specific example of a method for quantifying the terminal group concentration of a polyamide resin, a method described in the example of Japanese Patent Laid-Open No. 07-228689 can be cited. Specifically, in terms of accuracy and simplicity, the number of each terminal group is preferably determined by ¹ H-NMR (500 MHz, measured in deuterated trifluoroacetic acid at 50 ° C.) according to each terminal group. Calculate the integral value of the corresponding characteristic signal. When the characteristic signal of the terminal sealed by the blocking agent cannot be identified, the limiting viscosity [η] of the polyamide resin can be measured, and the total number of molecular chain terminal groups can be calculated using the relationship of the following formula.

Mn = 21900 [η] -7900 (Mn stands for number average molecular weight)

Total number of molecular chain terminal groups (eq / g) = 2 / Mn

Preferably, 10 to 95% of the terminal groups of the molecular chain of the polyamide resin are sealed with a capping agent. The ratio of the terminal groups of the molecular chain of the polyamide resin to be sealed (blocking ratio) is more preferably 40% or more, and still more preferably 60% or more. By setting the blocking ratio within the above range, it is possible to further effectively suppress the viscosity change during the melt molding of the thermoplastic resin composition, and further improve the surface appearance of the obtained molded product or the heat resistance stability during processing. The end-capping ratio is preferably 95% or less, and more preferably 90% or less. By setting the blocking ratio within the above range, the impact resistance and the surface appearance of the molded article are further improved.

The blocking ratio of the polyamide resin (E1) can be determined by measuring the number of terminal carboxyl groups, terminal amine groups, and terminal groups sealed by a blocking agent in the polyamide resin, and according to the following formula (I) Find it.

Capping rate (%) = [(α-β) / α] × 100 (I)

(In the formula, a represents the total number of terminal groups of the molecular chain (unit = Mole; it is usually equal to 2 times the number of polyamine molecules), β represents the total amount of carboxyl and amine groups remaining unsealed. (Unit = Mor)

The terminal blocking agent is not particularly limited as long as it is a monofunctional compound having reactivity with an amine group and / or a carboxyl group at the terminal of a polyamide resin, from the viewpoints of reactivity and stability of the sealed terminal, etc. In other words, monocarboxylic acids and monoamines are preferred, and from the standpoint of ease of handling, monocarboxylic acids are more preferred. In addition, acid anhydrides, monoisocyanates, Terbium halides, monoesters, monoalcohols, etc. are used as end-capping agents.

The monocarboxylic acid used as a capping agent is not particularly limited as long as it has reactivity with an amine group, and examples thereof include acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, caprylic acid, and lauric acid. Aliphatic monocarboxylic acids such as tridecyl acid, myristic acid, palmitic acid, stearic acid, pivalic acid, isobutyric acid; alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid; benzoic acid, toluic acid, α -Aromatic monocarboxylic acids such as naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, phenylacetic acid; any mixtures thereof, and the like. Among these, acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, caprylic acid, lauric acid, tridecanoic acid, and meat are preferred from the viewpoints of reactivity, stability of the sealed end, and economy. Myristic acid, palmitic acid, stearic acid, and benzoic acid, more preferably acetic acid and benzoic acid.

The monoamine used as a capping agent is not particularly limited as long as it has reactivity with a carboxyl group, and examples thereof include methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, Aliphatic monoamines such as stearylamine, dimethylamine, diethylamine, dipropylamine, and dibutylamine; alicyclic monoamines such as cyclohexylamine, dicyclohexylamine; aniline, toluidine, diphenylamine, naphthylamine, etc. Aromatic monoamines; any mixtures of these. Among these, butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine, and aniline are preferred from the viewpoints of reactivity, boiling point, stability of the sealed end, and economy, etc. More preferred are butylamine, hexylamine, and octylamine.

In order to further improve the heat resistance stability of the thermoplastic resin composition, not only the polyamide resin (E1) but also a transition metal (except iron) or a halogen may be present in the thermoplastic resin composition.

The type of the transition metal (except iron) is not particularly limited as long as it is other than iron. Examples include copper, cerium, nickel, and cobalt. Among these, from the viewpoint of long-term thermal stability, it is preferably copper. The type of halogen is not particularly limited, and bromine and iodine are preferred from the viewpoint of preventing corrosion of production equipment and the like.

When the total amount of the thermoplastic resin composition is 100% by mass, the content of the transition metal (excluding iron) is preferably 1 ppm or more, more preferably 5 ppm or more on a mass basis. It is preferably less than 200 ppm, and more preferably less than 100 ppm.

When the total amount of the thermoplastic resin composition is 100% by mass, the content of halogen is preferably 500 ppm or more, more preferably 700 ppm or more on a mass basis. It is preferably less than 1500 ppm, and more preferably less than 1200 ppm.

The method for adding such transition metals (except iron) or halogens to the thermoplastic resin composition is not particularly limited, and examples thereof include the same as that in which the polyamide resin (E1) and the polyphenylene ether (A) are added. The method of adding powder in the step of melt-kneading; the method of adding during polymerization of the polyamide resin (E1); the mother of the polyamide resin (E1) added with a high concentration of transition metal or halogen A method of adding the master batch particles of the polyamide resin (E1) to the thermoplastic resin composition after the pellets are prepared. Among these methods, a preferable method is a method for adding the polyamide resin (E1) during polymerization, and a method in which a transition metal and / or a halogen is added to the polyamide resin (E1) at a high concentration. Method for adding after masterbatch particles.

From the viewpoint of further reducing the amount of deformation in a high-temperature environment, the content of the polyamide resin (E1) in the thermoplastic resin composition is preferably 50% by mass or less, and more preferably 40% by mass or less. From the viewpoint of further reducing the amount of deformation in a high-temperature environment, when the total mass of the polyphenylene ether (A), the styrene resin (B), and the glass fiber (C) is 100% by mass, the polymer The content of the amine-based resin (E1) is preferably 80% by mass or less.

-Polyphenylene sulfide resin (E2)-

Polyphenylene sulfide (hereinafter, sometimes simply referred to as "PPS") is a polymer containing repeating units of phenylene sulfide represented by the following general formula (4). The content of the repeating unit in the polyphenylene sulfide is preferably 50 mol% or more, more preferably 70 mol% or more, and even more preferably 90 mol% or more.

[-Ar-S-] (4)

(In the general formula (4), S represents a sulfur atom, and Ar represents an arylene group.)

Examples of the above-mentioned arylene include p-phenylene, m-phenylene, substituted phenylene (as a substituent, an alkyl group having 1 to 10 carbon atoms and phenyl group), p, p'- Biphenylphenylene Group, p, p'-phenylene, p, p'-phenylenecarbonyl, naphthyl and the like.

PPS is a homopolymer composed of only repeating units represented by the general formula (4), and may be a homopolymer composed of Ar in the general formula (4) composed of only one type of arylene. From the viewpoint of processability and heat resistance, although it may be composed of only repeating units represented by the general formula (4), Ar in the general formula (4) may be two or more different arylene groups. Copolymer. Among these, from the viewpoint of being excellent in processability and heat resistance and being easily available, it is preferably at least 50 mol%, more preferably at least 70 mol%, and even more preferably 90 mol. % PPS of p-phenylene sulfide repeating unit.

From the viewpoint of suppressing corrosion, the chlorine-containing concentration of PPS is preferably 1500 ppm or less, and more preferably 900 ppm or less. The chlorine concentration can be measured in accordance with JPCA-ES01 (halogen-free copper foil laminated board test method) specified by the Japan Printed Circuit Industry Association (JPCA). The analysis method can be performed by a flask combustion treatment ion chromatography.

The manufacturing method of PPS is not specifically limited, A well-known method can also be used. Examples include a method of polymerizing a halogen-substituted aromatic compound (for example, p-dichlorobenzene, etc.) in the presence of sulfur and sodium carbonate; sodium sulfide or sodium sulfide, sodium hydroxide or hydrogen sulfide, and hydroxide Polymerization in a polar solvent in the presence of sodium or sodium aminoalkanoate; self-condensation of parachlorothiophenol. Among these, more specifically, sodium sulfide and p-dichlorobenzene are preferably used in an ammonium-based solvent such as N-methylpyrrolidone and dimethylacetamide or an ammonium-based solvent such as cyclobutane. How to react. In order to make the molecular chain form a branched structure, trichlorobenzene can also be used as a branching agent as needed.

PPS can also use, for example, U.S. Patent No. 2513188, Japanese Patent Publication No. 44-27671, Japanese Patent Publication No. 45-003368, Japanese Patent Publication No. 52-012240, and Japanese Patent Publication No. 61-225217. No., US Patent No. 3274165, Japanese Patent Publication No. 46-027255, Belgian Patent No. 29437, Japanese Patent Laid-Open No. 05-222196, and other methods. The PPS obtained in such a polymerization reaction is usually a linear PPS.

In this embodiment, it is also possible to promote oxidative cross-linking by performing a heat treatment at a temperature below the melting point of PPS (for example, 200 to 250 ° C.) in the presence of oxygen after the polymerization reaction is performed, and to appropriately increase the molecular weight of the polymer. Or viscosity (crosslinked PPS). A semi-crosslinked PPS having a lower degree of crosslinking is also included in the crosslinked PPS.

The melt viscosity of 300 ° C at a shear rate of 100 seconds ^-1 of PPS is preferably 10 Pa · s or more. In addition, it is preferably 150 Pa · s or less, more preferably 100 Pa · s or less, and even more preferably 80 Pa · s or less. By setting the melt viscosity within the above range, the balance between toughness and rigidity can be maintained at a higher level, and the occurrence of burrs during molding can be further effectively suppressed.

Furthermore, the melt viscosity can be measured by a capillary rheometer. For example, Capilograph (manufactured by Toyo Seiki Seisakusho Co., Ltd.) can be used for measurement under conditions of a temperature of 300 ° C and a shear rate of 100 seconds ^-1 using a capillary tube (capillary length = 10 mm, capillary diameter = 1 mm).

As specific examples of the PPS, the linear PPS, the cross-linked PPS, and the like described above may be used alone or in combination of two or more. The combination of linear PPS and cross-linked PPS as PPS is preferred because it can reduce the particle size of the dispersed phase of polyphenylene ether when making an alloy of PPS and polyphenylene ether.

From the viewpoint of reducing whitening or mold deposit during molding, the content of the oligomer contained in the PPS is preferably 0.7% by mass or less. Here, the oligomer contained in PPS means a substance extracted from PPS by dichloromethane, and is a substance generally treated as an impurity of PPS.

The content of the oligomer can be measured by the following method. 5 g of PPS powder was added to 80 mL of dichloromethane, and after performing Soxhlet extraction for 6 hours, it was cooled to room temperature, and the dichloromethane solution as an extract was transferred to a weighing bottle. Then, a total of 60 mL of dichloromethane was used, and the container for extraction was washed three times, and the washing solution was added to the extraction solution in the weighing bottle and recovered. Then, the extract was heated at about 80 ° C, the methylene chloride was evaporated to remove it, and the residue was recovered. Weigh the residue, and by measuring the amount of residue, you can obtain the The ratio of the amount of extraction (ie, the amount of oligomers present in the PPS).

From the viewpoint of further reducing the amount of deformation under a high temperature environment, the content of PPS (E2) in the thermoplastic resin composition is preferably 50% by mass or less, and more preferably 40% by mass or less. From the viewpoint of further reducing the amount of deformation in a high-temperature environment, when the total mass of the polyphenylene ether (A), the styrene resin (B), and the glass fiber (C) is 100% by mass, the PPS ( The content of E2) is preferably 60% by mass or less.

-other materials-

The thermoplastic resin composition may contain stabilizers such as antioxidants, ultraviolet absorbers, heat stabilizers, colorants, release agents, and the like within a range that does not significantly reduce mechanical properties, flame retardancy, and surface appearance of the molded body. .

When the total mass of polyphenylene ether (A), styrene-based resin (B), glass fiber (C), and organic phosphorus-based flame retardant (D) is 100% by mass, the content of the above-mentioned antioxidants and the like From the standpoint of expressing their sufficient additive effects, it is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, still more preferably 0.2% by mass or more, and maintaining the physical properties of the thermoplastic resin composition described above. From a viewpoint, it is preferably 3% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less.

The said thermoplastic resin composition may contain the inorganic filler other than glass fiber (C) in the range which does not significantly reduce mechanical physical properties, impact resistance, and flame retardance.

The inorganic filler other than the glass fiber (C) is not limited to the following, and examples thereof include carbon fiber, mica, talc, glass flakes, glass milled fibers (those made by grinding glass fibers into powder), Chlorite and so on.

When the total mass of polyphenylene ether (A), styrene-based resin (B), glass fiber (C), and organic phosphorus-based flame retardant (D) is 100% by mass, rigidity and durability are provided. From the viewpoint, the content of the inorganic filler other than the glass fiber (C) is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 10% by mass or less, and even more preferably 8% by mass. the following.

From the viewpoint of metal corrosivity, the total mass of the polyphenylene ether (A), the styrene resin (B), and the glass fiber (C) in the thermoplastic resin composition is 90% by mass or more, and the total mass is When it is set to 100% by mass, it is preferable to contain 25 to 75% by mass of polyphenylene ether (A), 0 to 5% by mass of styrene resin (B), and 20 to 50% by mass of glass fiber (C). Contains 45 to 75% by mass of polyphenylene ether (A), 0 to 5% by mass of styrene resin (B), and 25 to 50% by mass of glass fiber (C).

From the viewpoint of obtaining a fan-shaped product with less deformation in a high-temperature environment, the total of the polyphenylene ether (A), the styrene-based resin (B), and the glass fiber (C) in the thermoplastic resin composition The mass is preferably 85% by mass or more, and more preferably 90% by mass or more.

[Manufacturing method of thermoplastic resin composition]

The thermoplastic resin composition can be obtained by, for example, polyphenylene ether (A), polyphenylene ether (B), glass fiber (C), organic phosphorus-based flame retardant (D), polyamide resin (E1), The phenyl sulfide resin (E2) and other materials are produced by melt-kneading.

In the above thermoplastic resin composition, when the organic phosphorus-based flame retardant (D) is a compound having a melting point of 35 to 60 ° C. and is a solid or a powder at ordinary temperature, the thermoplastic resin composition may be extruded. When the raw material input port of the machine or the raw material feed line near the barrel, the component (D) is melted and fixed, so the line may be blocked and the production may be interrupted. When manufacturing the said thermoplastic resin composition, it is preferable to use the manufacturing method which eliminates this problem.

The manufacturing method of the said thermoplastic resin composition is not limited to the following, For example, it is preferable to mix an organophosphorus flame retardant (D) and a part or all of polyphenylene ether (A), and to prepare a mixture, and to mix this mixture Used as a raw material for thermoplastic resin composition. Here, regarding the mixing ratio of the organic phosphorus-based flame retardant (D) and the polyphenylene ether (A) in the mixture, the organic phosphorus-based flame retardant is considered from the viewpoint of workability when producing a thermoplastic resin composition. The mass of the polyphenylene ether (A) when the mass of (D) is set to 1 is preferably 1 or more, more preferably 1.5 or more, and even more preferably 2 or more. Increase in production From the viewpoint of complexity, it is preferably set to 7 or less, more preferably set to 6 or less, and even more preferably set to 5 or less.

The preparation of a mixture containing an organic phosphorus-based flame retardant (D) and polyphenylene ether (A) is not limited to the following. For example, a stirrer capable of adjusting the stirring speed or a Henschel capable of adjusting the speed of a rotating blade can be used. The mixer can prepare the mixture while adjusting the conditions such as speed, temperature, and time according to the properties (solid, powder, etc.) of the organic phosphorus flame retardant (D).

Regarding the method for producing the thermoplastic resin composition, a biaxial extruder can be preferably used from the viewpoint of stably producing a large amount of the thermoplastic resin composition, that is, the viewpoint of production efficiency, but it is not limited to the above.

Examples of the twin-shaft extruder include a ZSK40MC twin-shaft extruder (manufactured by Werner & Pfleiderer, Germany, number of barrels 13, screw diameter 40 mm, L / D = 50; kneading discs L (left): 2 kneading discs R (right-handed): 6 and kneading discs N (bidirectional): 4 screw models), which can be used at a cylinder temperature of 270 ~ 330 ° C, screw revolutions of 150 ~ 450rpm, and extrusion rate of 40 ~ Melt and knead at 220kg / h. Examples of the twin-shaft extruder include a TEM58SS twin-shaft extruder (manufactured by Toshiba Machine Co., the number of barrels is 13, the diameter of the screw is 58 mm, and L / D is 53; the number of kneading disks L is 2; : 14 and kneading disc N: 2 screw type), it can also be used under the conditions of cylinder temperature of 270 ~ 330 ℃, screw rotation number of 150 ~ 500rpm, extrusion rate of 200 ~ 600kg / h Melt and mix.

Here, the "L" of the L / D is the "screw barrel length" of the extruder, and the "D" is the "diameter of the screw barrel".

The screw diameter of the biaxial extruder is preferably set to 25 to 90 mm, and more preferably set to 40 to 70 mm.

When manufacturing the said thermoplastic resin composition using a biaxial extruder, a polyphenylene ether (A), a styrene resin (B), and a polyphenylene ether (A), and a polystyrene ether (B) are preferable at the point which gives heat resistance and mechanical physical properties to a material The organophosphorus flame retardant (D) is from the supply port (top) of the most upstream part of the extruder. Part feed), glass fiber (C) is supplied from the supply port (side feed) in the middle of the extruder.

[Fan molding]

The fan-molded article of this embodiment can be obtained by molding the above-mentioned thermoplastic resin composition. Examples of the molding method include compression molding, injection molding, calendar molding, extrusion molding, hollow molding, inflation molding, thermoforming, and blow molding.

The maximum diameter of the fan molded product of this embodiment is preferably 30 mm or more, more preferably 40 mm or more, more preferably 200 mm or less, more preferably 160 mm or less, and even more preferably 120 mm or less. When the maximum diameter is 200 mm or less, miniaturization of an electronic device to which a fan molded product is applied can be achieved.

The fan molded product of this embodiment is preferably used as an electronic device such as a server, a communication device such as a mobile phone base station, and a power supply device for a vehicle (for example, a lithium-ion battery, a nickel-metal hydride battery, and the like in an electric vehicle, a hybrid vehicle, and the like). Cooling fan, etc.

If the size of the electronic device is reduced, heat can easily accumulate inside the electronic device. The fan-molded product of this embodiment is a fan-molded product made of a thermoplastic resin composition in a specific range of E2 '/ E1' and E2 '/ ρ. Therefore, it is difficult to deform even under high heat and high-speed rotation, and it can also be applied. Inside small electronic equipment that can accumulate heat easily. In addition, even under high heat and high-speed rotation, the cooling efficiency is high.

[Example]

Hereinafter, specific examples and comparative examples of the present invention will be described. The present invention is not limited by these.

The methods for measuring the raw materials and physical properties of the fan molded products of the examples and comparative examples are shown below.

[Raw materials]

-Polyphenylene ether (A)-

PPE-1: Specific viscosity η (measured at 30 ° C using chloroform solvent) 0.52dl / g Poly (2,6-dimethyl-1,4-phenylene) ether

PPE-2: Poly (2,6-dimethyl-1,4-phenylene) ether with reduced viscosity η (measured at 30 ° C using chloroform solvent) of 0.40 dl / g

PPE-3: Poly (2,6-dimethyl-1,4-phenylene) ether with reduced viscosity η (measured at 30 ° C using chloroform solvent) of 0.31 dl / g

-Polystyrene (B)-

GPPS-1: General-purpose polystyrene (trade name: Styron660 (registered trademark), manufactured by Dow Chemical, USA)

-Glass fiber (C)-

GF-1: Glass fiber with an average fiber diameter of 10 μm and a fiber cut length of 3 mm after surface treatment with an amine silane compound (trade name: EC10 3MM 910 (registered trademark), manufactured by NSG Vetrotex)

GF-2: Glass fiber with an average fiber diameter of 13 μm and a fiber cut length of 3 mm after surface treatment with an amine silane compound (trade name: ECS03T-249 (registered trademark), manufactured by Nippon Electric Glass Co., Ltd.)

-Organic phosphorus flame retardant (D)-

FR-1: Triphenyl phosphate (aromatic phosphate-based flame retardant, trade name: TPP (registered trademark), manufactured by Big Eight Chemical Co., Ltd.)

FR-2: bisphenol A bis (diphenyl phosphate) (aromatic phosphate ester flame retardant, trade name: CR-741 (registered trademark), manufactured by Big Eight Chemical Co., Ltd.)

FR-3: phenylphosphanate (phosphazene flame retardant, trade name: Rabitle (registered trademark) FP-110, manufactured by Fushimi Pharmaceutical Co., Ltd.)

-Polyamine resin (E1)-

PA9T-1: Polyamine (According to the method described in the example of Japanese Patent Laid-Open No. 2000-212433, 3279.96 g (19.7 moles) of terephthalic acid as a dicarboxylic acid component and a diamine component are used. 1,253-64,1,9-nonanediamine (16.0 mol) and 633.16 g (4.0 mol) of 2-methyl-1,8-octanediamine, 73.26 g (0.60 mol) of benzoic acid as a capping agent 6.5 g of sodium hypophosphite monohydrate (0.1% by mass relative to the raw material) and 6 liters of distilled water were put into an autoclave with an internal volume of 20 liters and replaced with nitrogen. Stirring at 100 ° C for 30 minutes, it took 2 hours to remove the inside The temperature was raised to 210 ° C. At this time, the autoclave was boosted to 22kg / cm ^2. Under this condition, the reaction was continued for 1 hour, and then the temperature was raised to 230 ° C. After that, the temperature was maintained at 230 ° C and released slowly. The reaction was carried out while maintaining the pressure at 22 kg / cm ^{2 with} water vapor. Then, it took 30 minutes to reduce the pressure to 10 kg / cm ² and allowed to react for 1 hour to obtain a preliminary viscosity [η] of 0.25 dl / g. The polymer was dried at 100 ° C under reduced pressure for 12 hours, and pulverized to a size of 2 mm or less. It was subjected to solid-phase polymerization at 230 ° C under 0.1 mmHg for 10 hours. To obtain a granular polymer of polyamide. Using a biaxial extruder with a cylinder temperature of 330 ° C, a granular PA9T-1 was obtained from the obtained granular polymer. Melting point: 304 ° C, Limiting viscosity [η]: 1.20 dl / g, capping rate: 90%, terminal amine group concentration: 10 μmol / g, terminal carboxyl group 60 μmol / g, phosphorus element content: 300 ppm)

-Polyphenylene sulfide resin (E2)-

PPS-1: Polyphenylene sulfide (DSP (registered trademark) K-2G, manufactured by DIC EP Co., Ltd.)

-other materials-

PBT-1: Polybutylene terephthalate (Duranex PBT (registered trademark) 2002, manufactured by WinTech Polymer Co., Ltd.)

FR-4: Aluminum dialkylphosphinate (metal phosphinate flame retardant, trade name: Exolit OP1230 (registered trademark), manufactured by Clariant Japan)

FR-5: brominated polystyrene (brominated flame retardant, trade name: SAYTEX (registered trademark) HP-7010, manufactured by Albemarle Japan)

Phase solvent-1: styrene-glycidyl methacrylate copolymer containing 5% by weight of glycidyl methacrylate (weight average molecular weight 110,000)

Phase solvent-2: Trade name: CRYSTAL MAN AB (registered trademark), Japan Oil & Fat Co., Ltd.

Antimony trioxide: Trade name: PATOX-M (registered trademark), manufactured by Japan Concentrate Co., Ltd.

Mica: Trade name: C-1001F (registered trademark), manufactured by Repco

[Evaluation]

(1) Storage elastic modulus

1. Make a measurement sample

A part of the impeller of the fan molded product manufactured in the examples and comparative examples was cut out, and a test piece having a length of 50 mm, a width of 10 mm, and a thickness of 4 mm was produced by hot pressing.

2. determination

Using a dynamic viscoelasticity measuring device (trade name "Eplexor 500N", manufactured by ITS-JAPAN Co., Ltd.), the storage elastic modulus at 85 ° C and the storage elastic modulus at 110 ° C were measured under the following conditions.

(2) UL94 flammability

Using a short strip-shaped molded piece with a thickness of 0.75 mm, the flame retardancy rating was determined based on the flame retardancy test specification UL94.

(3) Fan deformation

As shown in FIG. 5, the rotating shaft is passed through an aluminum box 3 (in a heat-insulating box) installed in an air-supply constant temperature thermostat (type DKM600, manufactured by Yamato Scientific Co., Ltd.). An evaluation fan molded product 1 connected to a DC (direct current) brushless motor 2 (BMS-4020, manufactured by Nakanishi) was set, and a rotation test was performed.

First, at a temperature of 25 ° C, the fan-shaped product 1 is rotated at 1,000 rpm, and a laser sensor (Keyence, IB-10) is used to continuously measure the outermost part of the fan and simulate the actual product. The gap length of the aluminum box 3 with an inner diameter of Φ120mm. When the value is stable, the gap length (L1 (mm)) from the aluminum box 3 is obtained.

Next, the temperature of the thermostat was set to 85 ° C. When the temperature was stable, the number of revolutions of the fan molded product 1 was set to 7,000 rpm, and the outermost part of the fan was continuously measured by a laser sensor (emitter 4 and receiver 5) The length of the gap with the aluminum box 3 with an inner diameter of Φ120mm that simulates the actual product. When the value is stable, find the gap length (L2 (mm)) from the aluminum box.

The amount of deformation of the fan is obtained by the following formula.

"Fan deformation: 85 ° C x 7,000 rpm (mm)" = L2-L1

The amount of fan deformation at a temperature of 110 ° C and a rotation speed of 7,000 rpm was also calculated by the same method.

(4) Corrosiveness of mold steel

The granular thermoplastic resin composition described in Table 1 was put into a ceramic crucible (inner diameter Φ38mm, height 110mm), and the carbon steel S55C cut into a size of 20mm in width, 40mm in length, and 3mm in thickness was embedded in the granules sheet. The ceramic crucible containing the resin particles and the carbon steel sheet was allowed to stand in an electric furnace at 330 ° C for 5 hours, and after taking out, it was cooled to normal temperature by a dryer. After cooling, the carbon steel sheet was taken out from the resin material, and the presence or absence of corrosion on the surface was visually confirmed. The case where no corrosion was observed was evaluated as "none", and the case where corrosion was observed was evaluated as "yes".

[Example 1]

Self-biaxial extruder (trade name: ZSK40MC, manufactured by Werner & Pfleiderer, the number of barrels is 13, screw diameter is 40mm, with kneading discs L: 2, kneading discs R: 6, kneading disc N: 4 ) (Upper feed) supply (PPE-1) 34 Parts by mass and (FR-1) / (PPE-1) = 1/3 in advance using a Henschel mixer to stir and mix (revolutions 600rpm, stirring time 1min, internal temperature 23-25 ° C) 36 parts by mass of the mixture, 30 parts by mass of (GF-1) were fed from the middle of the barrel 8 and melt-kneaded at a cylinder temperature of 300 ° C, a screw revolution of 250 rpm, and an extrusion rate of 100 kg / h to obtain a thermoplastic resin combination. Thing.

The specific gravity ρ of the thermoplastic resin composition at 23 ° C. is measured in accordance with ISO 1183.

A 3D scan was performed on the axial flow fan (model "9GV1212P1J01", manufactured by Shanyang Electric Co., Ltd.) to convert the shape of the fan into CAD (Computer Assisted Design) data. Based on the obtained CAD data, a mold for injection molding of a fan molded product is produced. The maximum diameter of the mold fan produced was 114mm.

Using the mold and an injection molding machine (trade name: EC100SX, manufactured by Toshiba Machinery Co., Ltd.), the thermoplastic resin composition was molded under the temperature conditions described in Table 1 to obtain a fan molded product.

In addition, in Comparative Example 3 (PPS material), after forming, it was left to stand in a 150 ° C. oven for 3 hours to perform an annealing treatment.

[Examples 2 to 9, Comparative Examples 1 to 4]

A fan-molded article was obtained in the same manner as in Example 1 except that the composition of the thermoplastic resin composition was set to the composition described in Table 1 and the molding temperature was set to the temperature described in Table 1.

[Industrial possibilities]

According to the fan molded product of the present invention, even if the fan is operated in a high-temperature environment and in a high-rotation state, it is possible to obtain a fan molded product that has less deformation of the fan, can rotate at a higher speed, and has higher cooling efficiency.

Claims (10)

A fan molded product comprising a thermoplastic resin composition including a ratio of a storage elastic modulus E2 'at 110 ° C to a storage elastic modulus E1' at 85 ° C in a dynamic viscoelasticity measurement of the thermoplastic resin composition. (E2 '/ E1') is 0.90 or more, and the specific storage elastic modulus (E2 '/ ρ) when the storage elastic modulus at 110 ° C is set to E2' and the specific gravity at 23 ° C is set to ρ is 4,000. Above MPa. The fan molded product according to claim 1, wherein the flame retardancy rating of the thermoplastic resin composition (implemented with a test piece thickness of 0.75 mm based on UL94) is V-0. If the fan-shaped product of claim 1 has a maximum diameter of 200 mm or less. If the fan-shaped product of claim 2 has a maximum diameter of 200 mm or less. The fan-molded article according to any one of claims 1 to 4, wherein the thermoplastic resin composition is a polyphenylene ether-based resin composition. The fan molded product according to claim 5, wherein the thermoplastic resin composition is a polyphenylene ether-based resin composition: the total mass of the polyphenylene ether (A), the styrene-based resin (B), and the glass fiber (C). When it is 90% by mass or more and the total mass is 100% by mass, it contains 45 to 75% by mass of polyphenylene ether (A), 0 to 5% by mass of styrene resin (B), and 25% by weight of glass fiber (C) ~ 50% by mass. The fan molded product according to claim 5, wherein the thermoplastic resin composition further contains an organic phosphorus-based flame retardant (D), and the polyphenylene ether (A), the styrene-based resin (B), the glass fiber (C), and When the total mass of the organic phosphorus-based flame retardant (D) is 100% by mass, the content of the organic phosphorus-based flame retardant (D) is 5 to 20% by mass. The fan molded article according to claim 6, wherein the thermoplastic resin composition further contains an organic phosphorus-based flame retardant (D), and the polyphenylene ether (A), the styrene-based resin (B), the glass fiber (C), and When the total mass of the organic phosphorus-based flame retardant (D) is 100% by mass, the content of the organic phosphorus-based flame retardant (D) is 5 to 20% by mass. For example, the fan molded article of claim 7, wherein when the mass of the organic phosphorus-based flame retardant (D) is 100% by mass, the organic phosphorus-based flame retardant (D) contains a material selected from the group consisting of triphenyl phosphate and phosphazene 70% by mass or more of one or more compounds in the composed group. For example, the fan molded article of claim 8, wherein when the mass of the organic phosphorus-based flame retardant (D) is 100% by mass, the organic phosphorus-based flame retardant (D) contains a material selected from the group consisting of triphenyl phosphate and phosphazene 70% by mass or more of one or more compounds in the composed group.