JP6231429B2 - Polyphenylene ether-based resin composition and molded body, and method for producing polyphenylene ether-based resin composition - Google Patents

Description

  The present invention relates to a polyphenylene ether-based resin composition and a molded body, and a method for producing a polyphenylene ether-based resin composition.

  The polyphenylene ether-based resin is usually a combination of a polyphenylene ether and a styrene-based resin in a proportion corresponding to the required heat resistance and molding fluidity level, and further, if necessary, an elastomer component, Additive components such as a flame retardant, an inorganic filler, and a heat stabilizer are blended to obtain a polyphenylene ether resin composition.

  Polyphenylene ether resins are excellent in heat resistance, mechanical properties, molding processability, acid / alkali resistance, dimensional stability, electrical characteristics, and the like, and thus are widely used in home appliances OA, office machines, information equipment, automobile fields, and the like. Among these uses are cooling fans (propellers) for electrical and electronic equipment such as home appliances OA, office machines and PCs, etc., in recent years, as extremely thin heat-formed products, bending strength, tensile strength, etc. Mechanical properties such as strength are required, and many of them require durability to withstand long-term stresses under high temperature conditions. Polyphenylene containing a large amount of inorganic fillers, especially glass fibers. Ether-based resin compositions have been studied.

  On the other hand, in recent years, an extremely high flame retardant level that has not been conventionally required is often required for such applications, and a polyphenylene ether resin composition in which a large amount of an inorganic filler such as glass fiber is blended with a polyphenylene ether resin. Furthermore, it is known that a certain amount of flame retardancy can be achieved by blending a flame retardant (see, for example, Patent Documents 1 and 2). However, since the fibrous inorganic filler has a wick effect, it is extremely difficult to add a flame retardant to a resin composition containing a large amount of glass fiber to make it flame retardant to a high level. It is also known that even if the amount of the flame retardant is increased, it is difficult to further increase the flame retardancy (see, for example, Patent Document 3).

JP-A-8-183902 JP-A-10-168260 JP-T-2001-500182

As mentioned above, it is extremely difficult to add a flame retardant to a resin composition containing a large amount of glass fiber to make it flame retardant to a high level. However, it is difficult to make it more flame retardant. In addition, when a large amount of flame retardant is blended, mechanical properties such as tensile strength and bending strength that are increased by blending a large amount of glass fiber may decrease significantly, so the target performance is finally reached. A balance material is difficult to achieve, and heretofore has not been realized with known polyphenylene ether resin compositions.
Therefore, the present invention can sufficiently withstand use as a thin molded article such as a cooling fan for electric and electronic equipment, mechanical properties such as extremely high tensile strength, bending strength, impact strength, advanced flame retardancy, sufficient It is an object of the present invention to provide a polyphenylene ether-based resin composition having molding fluidity. Another object of the present invention is to provide a molded article comprising the polyphenylene ether-based resin composition. Furthermore, this invention also aims at providing the manufacturing method of the said polyphenylene ether-type resin composition.

  The present inventors have intensively studied to develop a polyphenylene ether-based resin composition that has mechanical properties such as tensile strength, bending strength, impact strength, and further high flame retardancy and sufficient molding fluidity. As a result, 20-50 mass% of glass fiber is contained as an inorganic filler, the content of the styrene resin is adjusted to 5 mass% or less, and a specific flame retardant is further blended to make the flame retardant. By finding a polyphenylene ether-based resin composition that can be used effectively for applications such as cooling fans for electrical and electronic equipment, achieving both unprecedented good mechanical properties and high flame retardancy, The present invention can be provided.

That is, the present invention
[1] A polyphenylene ether resin composition in which the total mass of polyphenylene ether (A), styrene resin (B), glass fiber (C), and organophosphorus flame retardant (D) is 90% by mass or more. The total mass is 100% by mass, polyphenylene ether (A) 25-75% by mass, styrene resin (B) 0-5% by mass, glass fiber (C) 20-50% by mass, and organophosphorous flame retardant. (D) 5 to 20% by mass, 70% by mass or more of one or more compounds selected from the group consisting of triphenyl phosphate and phosphazene, with the mass of the organophosphorus flame retardant (D) being 100% by mass Containing polyphenylene ether resin composition,
[2] In the above [1], a polyphenylene ether-based resin composition having a tensile strength (according to ISO 527, measured at 23 ° C.) of 130 MPa or more,
[3] A polyphenylene ether-based resin composition according to any one of the above [1] and [2], wherein the flame retardancy level (conforms to UL94. Conducted with a tanzania test piece thickness 0.8 mm test piece) is V-0.
[4] In any one of [1] to [3] above, a polyphenylene ether-based resin composition having a flexural strength (based on ISO 178. measured at 23 ° C.) of 170 MPa or more,
[5] In any one of the above [1] to [4], a polyphenylene ether resin composition having a high-temperature tensile strength (based on ISO 527; measured at 110 ° C.) of 70 MPa or more,
[6] In any one of the above [1] to [5], the organic phosphorus flame retardant (D) is a mixture of an aromatic phosphate ester and phosphazene, and the organic phosphorus flame retardant (D) A polyphenylene ether-based resin composition containing 70 to 95% by mass of phosphazene with a mass of 100% by mass,
[7] In any one of the above [1] to [5] , the organophosphorus flame retardant (D) is triphenyl phosphate, and the total mass is 100 mass%, and the triphenyl phosphate is 5 to 13 mass. % Polyphenylene ether-based resin composition,
[8] The polyphenylene ether-based resin composition according to any one of [1] to [5] , wherein the organophosphorus flame retardant (D) is phosphazene,
[9] In any one of [1] to [8] above, a polyphenylene ether resin composition not containing the styrene resin (B),
[10] The organophosphorus flame retardant (D) and the polyphenylene ether (A) are blended in advance at a ratio of (D) / (A) = 1/1 to 1/7 to obtain a blend. A process for producing the polyphenylene ether-based resin composition according to any one of [1] to [9], including a step and a step of kneading the blend and glass fiber (C),
[11] A cooling fan for electrical / electronic equipment, comprising the polyphenylene ether-based resin composition according to any one of [1] to [9],
It is.

  According to the polyphenylene ether resin composition of the present invention, it is possible to provide a polyphenylene ether resin composition having excellent mechanical properties such as tensile strength, bending strength, impact strength, flame retardancy, and molding fluidity. This polyphenylene ether-based resin composition can be effectively used particularly as a thin molded article such as a cooling fan of an electric / electronic device. Moreover, according to the molded object of this invention, the effect of the said polyphenylene ether-type resin composition of this invention can be acquired. Furthermore, according to the method for producing a polyphenylene ether resin composition of the present invention, the polyphenylene ether resin composition of the present invention can be produced.

  Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. The present invention is not limited to the following description, and various modifications can be made within the scope of the gist thereof.

(Resin composition)
The resin composition of the present embodiment is a polyphenylene ether type in which the total mass of polyphenylene ether (A), styrene resin (B), glass fiber (C), and organophosphorus flame retardant (D) is 90% by mass or more. It is a resin composition. From the viewpoint of sufficiently obtaining the effects of the present invention, the ratio is preferably 95% by mass or more, and more preferably 98% by mass or more.

  In the resin composition of the present embodiment, the total mass of the polyphenylene ether (A), the styrene resin (B), the glass fiber (C), and the organophosphorus flame retardant (D) is 100% by mass, and the polyphenylene ether (A ) 25 to 75% by mass, styrene resin (B) 0 to 5% by mass, glass fiber (C) 20 to 50% by mass, and organic phosphorus flame retardant (D) 5 to 20% by mass. A polyphenylene ether-based resin composition. Here, in the resin composition of the present embodiment, the mass of the organophosphorus flame retardant (D) is 100% by mass, and one or more compounds selected from the group consisting of triphenyl phosphate and phosphazene are 70% by mass or more. contains.

（上記一般式（１）、（２）中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵及びＲ⁶は、それぞれ独立して、炭素数１〜４のアルキル基、炭素数６〜１２のアリール基、その他の一価の基、例えば、ハロゲン及び水素等からなる群から選択される基である。但し、Ｒ⁵及びＲ⁶が共に水素である場合を除く。） -Polyphenylene ether (A)-
The polyphenylene ether (A) has a repeating unit represented by the following general formula (1) and / or (2), and the structural unit is a homopolymer (homopolymer) consisting of the general formula (1) or (2). It is preferable that it is a copolymer (copolymer) containing the structural unit of Formula (1) or (2).

(The above general formula (1), in ^{(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, 6 carbon atoms 12 aryl groups and other monovalent groups such as a group selected from the group consisting of halogen, hydrogen, etc., except that R ⁵ and R ⁶ are both hydrogen.)

  The other monovalent group is preferably hydrogen. Moreover, the hydrogen atom of the said alkyl group and the said aryl group may be substituted by the halogen, the hydroxyl group, and the alkoxy group. Furthermore, the preferable carbon number of the said alkyl group is 1-3, and the preferable carbon number of the said aryl group is 6-8.

  The number of repeating units in the general formulas (1) and (2) may vary depending on 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, but examples thereof include poly (2,6-dimethyl-1,4-phenylene) ether and poly (2-methyl-6- 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) 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 and the like, and in particular, from the viewpoint of easy availability of raw materials and processability, poly (2,6-dimethyl-1,4-phenylene) ether is preferable.

  Among the polyphenylene ethers (A), the copolymer is not limited to the following. For example, a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, 2,6 -Copolymers of dimethylphenol and o-cresol, and copolymers of 2,3,6-trimethylphenol and o-cresol, such as those mainly composed of polyphenylene ether, are available From the viewpoint of ease and processability, a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol is preferable, and from the viewpoint of improving physical properties, 2,6-dimethylphenol and 2,3,6 are preferable. -Copolymers with trimethylphenol (especially 90-70% by weight of 2,6-dimethylphenol moiety and 2,3,6-trimethylphenol moiety 1 Those containing 30 wt%) is more preferable.

  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 resin composition does not deteriorate too much, the polyphenylene ether (A) is a polyphenylene ether containing various phenylene ether units other than the general formulas (1) and (2) as a partial structure. May be included.
Such a phenylene ether unit is not limited to the following. For example, 2- (dialkylaminomethyl) -6 described in JP-A-01-297428 and JP-A-63-301222 is used. -Methylphenylene ether unit, 2- (N-alkyl-N-phenylaminomethyl) -6-methylphenylene ether unit and the like.

  In the polyphenylene ether (A), diphenoquinone or the like may be bonded to the main chain of the polyphenylene ether.

  Furthermore, the polyphenylene ether (A) is selected from the group consisting of acyl functional groups and carboxylic acids, acid anhydrides, acid amides, imides, amines, orthoesters, hydroxy, and ammonium carboxylates as part or all of the polyphenylene ethers. You may have the structure replaced with the functionalized polyphenylene ether by making it react (modify | modify) with the functionalizing agent containing 1 or more types of functional groups.

  The ratio (Mw / Mn value) between the weight average molecular weight Mw and the number average molecular weight Mn of the polyphenylene ether (A) is preferably 2.0 or more from the viewpoint of moldability of the resin composition. It is more preferably 5 or more, even more preferably 3.0 or more, and from the viewpoint of mechanical properties of the resin composition, it is preferably 5.5 or less, and 4.5 or less. Is more preferable, and it is still more preferable that it is 4.5 or less. In addition, the weight average molecular weight Mw and the number average molecular weight Mn are obtained from the polystyrene conversion molecular weight by GPC (gel permeation chromatography) measurement.

From the viewpoint of sufficient mechanical properties, the reduced viscosity of the polyphenylene ether (A) is preferably 0.25 dl / g or more, more preferably 0.30 dl / g or more, and 0.33 dl / g. g or more, and from the viewpoint of molding processability, it is preferably 0.65 dl / g or less, more preferably 0.55 dl / g or less, and 0.42 dl / g or less. Even more preferably. The reduced viscosity can be measured with a chloroform solvent, 30 ° C., and a 0.5 g / dl solution using an Ubbelohde viscometer.

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

-Styrenic resin (B)-
In the resin composition of the present embodiment, the styrene resin (B) is a polymer obtained by polymerizing a styrene compound in the presence or absence of a rubbery polymer, or a styrene compound and the styrene compound. A copolymer obtained by copolymerizing a copolymerizable compound in the presence or absence of a rubbery polymer.

The styrene compound refers to a compound in which one or more hydrogen atoms of styrene are substituted with a monovalent group.
Examples of the styrenic compound include, but are not limited to, styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, p-methylstyrene, p-tert-butylstyrene, and ethylstyrene. In particular, styrene is preferable from the viewpoint of the balance between the availability of raw materials of stable quality and the characteristics of the composition.

  The compound copolymerizable with the styrenic compound is not limited to the following. For example, methacrylic acid esters such as methyl methacrylate and ethyl methacrylate; unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile; Examples thereof include unsaturated acid anhydrides such as maleic anhydride.

Of the above styrene resins, a polymer or copolymer obtained by polymerization or copolymerization in the presence of a rubbery polymer is called a rubber-reinforced styrene resin, and in the absence of a rubbery polymer. A polymer or copolymer obtained by polymerization or copolymerization is referred to as a styrene resin not reinforced with rubber.
As the styrene resin (B) in the present invention, a styrene resin not reinforced with rubber is preferable from the viewpoint of mechanical properties of the molded article.

  In the resin composition of the present embodiment, the styrene resin (B) is preferably added from the viewpoint of improving the molding fluidity. The content of the styrene resin (B) in the total mass of 100% by mass of the polyphenylene ether (A), the styrene resin (B), the glass fiber (C), and the organophosphorus flame retardant (D). The amount is preferably 5% by mass or less and more preferably 3% by mass or less from the viewpoint of imparting sufficient heat resistance and flame retardancy.

-Glass fiber (C)-
Glass fiber (C) is mix | blended in the resin composition of this embodiment for the purpose of improving mechanical strength.

  As a kind of glass of glass fiber (C), a well-known thing can be used, for example, E glass, C glass, S glass, A glass, etc. are mentioned. Glass fiber (C) refers to fiber-shaped glass, and is distinguished from massive glass flakes and glass powder.

  The average fiber diameter of the glass fiber (C) is 5 μm or more from the viewpoints of deterioration of the rigidity, heat resistance, impact resistance, durability, etc. of the molded product due to fiber breakage during extrusion and molding and production stability. The thickness is preferably 7 μm or more, and is preferably 15 μm or less and more preferably 13 μm or less from the viewpoint of imparting sufficient mechanical properties and maintaining the appearance of the molded product surface.

  The average length of the glass fiber (C) is preferably 0.5 mm or more, more preferably 1 mm or more, more preferably 10 mm or less, and 6 mm or less from the viewpoint of handleability. It is more preferable.

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

  The glass fiber (C) used in the present embodiment may be surface-treated with a surface treatment agent such as a silane compound. The silane compound used for the surface treatment is usually used for surface treatment of glass fillers, mineral fillers, and the like. Specific examples of the silane compound include vinyl silane compounds such as vinyltrichlorosilane, vinyltriethoxysilane, and γ-methacryloxypropyltrimethoxysilane, epoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane, and bis- (3- Sulfur-based silane compounds such as triethoxysilylpropyl) tetrasulfide; mercaptosilane compounds such as γ-mercaptopropyltrimethoxysilane; aminosilane compounds such as γ-aminopropyltriethoxysilane and γ-ureidopropyltriethoxysilane In view of achieving the object of the present invention, aminosilane compounds are particularly preferred. These silane compounds may be used alone or in combination of two or more. Further, these silane compounds may be preliminarily mixed with a sizing agent such as an epoxy type or a urethane type, and surface-treated with the mixture.

The content of glass fiber (C) in the total mass of 100% by mass of polyphenylene ether (A), styrene resin (B), glass fiber (C), and organophosphorus flame retardant (D) is: From the viewpoint of improving the mechanical properties of the resin composition, it is preferably 20% by mass or more, more preferably 30% by mass or more, and from the viewpoint of imparting flame retardancy to the resin composition, 50% by mass. % Or less, more preferably 45% by mass or less .

-Organophosphorous flame retardant (D)-
The organophosphorus flame retardant (D) used in the resin composition of the present embodiment refers to a flame retardant composed of an organic compound containing phosphorus, a flame retardant composed of an inorganic compound containing phosphorus, and organic phosphoric acid and metal. Flame retardants consisting of these salts are not applicable.

Inclusion of organophosphorus flame retardant (D) in a total mass of 100% by mass of polyphenylene ether (A), styrene resin (B), glass fiber (C), and organophosphorus flame retardant (D) The amount is preferably 5% by mass or more from the viewpoint of improving the flame retardancy of the resin composition, more preferably 7% by mass or more, and 20% by mass from the viewpoint of maintaining heat resistance. Or less, more preferably 16% by mass or less.
Here, in the resin composition of this embodiment, 70 mass% or more of the organophosphorus flame retardant (D) is from the group consisting of triphenyl phosphate and phosphazene from the viewpoint of reducing environmental burden and imparting flame retardancy. One or more selected compounds.

  In addition, as an organophosphorus flame retardant (D), a phosphazene is preferable in the viewpoint of making it easy to acquire the effect of this invention in a triphenyl phosphate and a phosphazene.

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

（上記一般式（３）中、Ｘは、Ｐｈ（フェニル基）、又はＯＰｈ（フェニルオキシ基）を示す。） As phosphazene, what contains the structural unit shown to following General formula (3) is mentioned.

(In the general formula (3), X represents Ph (phenyl group) or OPh (phenyloxy group).)

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

  In the resin composition of the present embodiment, 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. The phosphazene is preferably a cyclic phenoxyphosphazene compound containing 70% by mass or more, preferably 85% by mass or more of the trimer, from the viewpoint of moldability and flame retardancy.

  When phosphazene is used alone as the organophosphorus flame retardant (D), the polyphenylene ether (A), the styrene resin (B), the glass fiber (C), and the organophosphorus flame retardant (D). The content of phosphazene in the total mass of 100% by mass is not particularly limited as long as it is 5 to 20% by mass described above.

In addition, less than 30 mass% of the organic phosphorus flame retardant (D) may be a compound other than triphenyl phosphate and phosphazene, for example, an aromatic phosphate other than triphenyl phosphate.
Examples of the aromatic phosphate ester include, but are not limited to, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, dixylenyl phenyl phosphate. Triphenyl-substituted aromatic phosphates such as hydroxynon bisphenol phosphate, resorcinol bisphosphate and bisphenol A bisphosphate are preferred, and triphenyl phosphate is more preferred.

  In the case of using a mixture of an aromatic phosphate ester and phosphazene as the organic phosphorus flame retardant (D), the resin composition of the present embodiment has a viewpoint of imparting better molding fluidity and mechanical properties. The mass ratio of the aromatic phosphate ester and phosphazene is preferably used in a combined ratio of 5:95 to 30:70, more preferably used in a combined ratio of 10:90 to 25:75, and 20:80 to 25 : More preferably, it is used at a combined ratio of 75.

-Other materials-
The resin composition of the present embodiment is a stabilizer such as an antioxidant, an ultraviolet absorber, a heat stabilizer, a colorant, and the like, as long as the mechanical properties, flame retardancy, and the surface appearance of the molded article are not significantly reduced. A release agent or the like may be included.
Content of the said antioxidant etc. made the total mass of polyphenylene ether (A), styrene resin (B), glass fiber (C), and organophosphorus flame retardant (D) 100 mass % . In this case, from the viewpoint of exhibiting a sufficient additive effect, it is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and further preferably 0.2% by mass or more. From the viewpoint of maintaining the physical properties of the resin composition of the present embodiment, it is preferably 3% by mass or less, more preferably 2% by mass or less, and further preferably 1% by mass or less. Is more preferable.

The resin composition of this embodiment may contain an inorganic filler other than the glass fiber (B) as long as the mechanical properties, impact resistance, and flame retardancy are not significantly reduced.
Examples of the inorganic filler other than the glass fiber (B) include, but are not limited to, for example, carbon fiber, mica, talc, glass flake, glass milled fiber (glass fiber crushed into powder form) ), Chlorite and the like.
The content of the inorganic filler other than the glass fiber (B) is the total mass of the polyphenylene ether (A), the styrene resin (B), the glass fiber (C), and the organophosphorus flame retardant (D). Is 100% by mass, from the viewpoint of imparting rigidity and durability, it is preferably 0.5% by mass or more, more preferably 1% by mass or more, and preferably 10% by mass or less. More preferably, it is 8 mass% or less.

[Method for producing resin composition]
The resin composition of the present embodiment can be produced by melt-kneading the component (A), the component (B), the component (C), the component (D), and other materials added as necessary. it can.

  In the resin composition of the present embodiment, the component (D) has a melting point of 35 to 60 ° C., and is a solid or powder compound at room temperature. The component (D) is melted in the raw material feed line or the like to produce a fixed substance, which may cause the blockage of the line and interrupt the production. In the production of the resin composition of the present embodiment, it is preferable to use a production method that eliminates this problem.

  The method for producing the resin composition of the present embodiment is not limited to the following, but for example, a blend is prepared by previously blending (D) component and part or all of (A) component. The blend is preferably used as a raw material for the resin composition. Here, regarding the ratio of the blend of the component (D) and the component (A) in the blend, when the component (D) is 1, the component (A) is easy to handle when producing the resin composition. From the viewpoint, it is preferably 1 or more, more preferably 1.5 or more, particularly preferably 2 or more, and from the viewpoint of reducing the complexity associated with an increase in the production amount of the blend. 7 or less, more preferably 6 or less, and particularly preferably 5 or less.

  The preparation of the blend containing the component (D) and the component (A) is not limited to the following. For example, a blender capable of adjusting the stirring speed and a Henschel mixer capable of adjusting the speed of the rotating blades. Depending on the properties (solid, powder, etc.) of component (D), the blend may be prepared while appropriately adjusting conditions such as speed, temperature and time.

In the method for producing a resin composition of the present embodiment, although not limited to the following, a twin-screw extruder is suitably used from the viewpoint of stably producing a resin composition in a large amount, that is, from the viewpoint of production efficiency. It is done.
As a twin screw extruder, for example, ZSK40MC twin screw extruder (manufactured by Werner & Pfleiderer, Germany, barrel number 13, screw diameter 40 mm, L / D = 50; kneading disk L (Left-handed): 2 pieces, kneading Disc R (Right-handed): 6 and kneading disc N (Neutral): screw pattern having 4), and using this, cylinder temperature 270-330 ° C., screw rotation speed 150-450 rpm, Melting and kneading can be performed under conditions of an extrusion rate of 40 to 220 kg / h. Moreover, as a twin screw extruder, for example, TEM58SS twin screw extruder (manufactured by Toshiba Machine Co., Ltd., barrel number 13, screw diameter 58 mm, L / D = 53; kneading disk L: 2 pieces, kneading disk R: 14 And a kneading disc N: a screw pattern having two pieces), and using this, melt kneading under conditions of a cylinder temperature of 270 to 330 ° C., a screw rotation speed of 150 to 500 rpm, and an extrusion rate of 200 to 600 kg / h. You can also
Here, “L” of L / D is “screw barrel length” of the extruder, and “D” is “diameter of screw barrel”.
The screw diameter of the twin screw extruder is preferably 25 to 90 mm, and more preferably 40 to 70 mm.

  When manufacturing the resin composition of this embodiment using a twin screw extruder, from the viewpoint of imparting heat resistance and mechanical properties to the material, the (A) component, the (B) component, and the (D) component are: It is preferable to supply from the supply port (top feed) of the most upstream part of an extruder, and to supply (C) component from the supply port (side feed) in the middle of an extruder.

= Physical properties =
Hereinafter, various physical properties of the resin composition of the present embodiment will be described.
The tensile strength (based on ISO 527, measured at 23 ° C.) of the resin composition of the present embodiment is desirably 130 MPa or more from the viewpoint of shape retention during use of the thin molded article and prevention of cracking. The tensile strength is preferably 135 MPa or more, more preferably 140 MPa or more.
The bending strength (based on ISO 178, measured at 23 ° C.) of the resin composition of the present embodiment is preferably 170 MPa or more from the viewpoint of shape retention during use of the thin molded article. The bending strength is more preferably 180 MPa or more, and even more preferably 190 MPa or more.
The Charpy (based on ISO 179. measured at 23 ° C.) of the resin composition of the present embodiment is 7 kJ / m from the viewpoint of preventing cracking of the thin molded article due to use under conditions where external force is applied, such as when the propeller rotates. It is preferably ² or more. Charpy is more preferably 10 kJ / m ² or more.
The flame retardancy level (based on UL-94) of the resin composition of this embodiment is V- in the implementation of a 0.8 mm thick tanzania test piece from the viewpoint of preventing the spread of fire due to ignition inside the apparatus of the thin molded article. 0 is desirable.
The MFR (based on ISO 1133. Measured at 250 ° C. and 10 kg load) of the resin composition of the present embodiment is preferably 3 g / 10 min or more from the viewpoint of moldability of the thin molded article. The MFR is more preferably 5 g / 10 min or more, and even more preferably 10 g / 10 min or more.
The DTUL (based on ISO75, measured by a flatwise method, measured by a 1.82 MPa load) of the resin composition of the present embodiment is preferably 100 ° C. or higher from the viewpoint of durability when the thin molded article is used at high temperatures. DTUL is more preferably 125 ° C. or higher, and even more preferably 135 ° C. or higher.
The high-temperature tensile strength (based on ISO 527, measured at 110 ° C.) of the resin composition of the present embodiment is preferably 70 MPa or more from the viewpoint of durability of the thin molded body at high temperatures. The high temperature tensile strength is more preferably 80 MPa or more.

[Molded body]
A molded body made of the resin composition of the present embodiment can be obtained by molding the above resin composition. The resin composition of the present embodiment is particularly suitable for forming a thin molded article. Here, the thin-walled molded product refers to a molded product having a thin-walled portion in the whole or a part of the molded product. The thin portion has a thickness of 3 mm or less, preferably 1.5 mm or less, more preferably 0.75 mm or less, and 1/20 or less of the length in two directions perpendicular to the thickness direction, preferably 1 / 100 or less, more preferably 1/500 or less.

  Suitable moldings include cooling fans for electric and electronic devices because they are required to have excellent heat resistance and mechanical strength and are extremely excellent in thin flame retardant properties.

  The method of molding the resin composition is not particularly limited, but for example, injection molding, extrusion molding, vacuum molding, and pressure molding are preferable, from the viewpoint of appearance characteristics and mass productivity of the molded body. Injection molding is particularly preferred.

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

  The raw material and the measuring method of the physical property of the resin composition of an Example and a comparative example are shown below.

〔raw materials〕
-Polyphenylene ether (A)-
PPE1: Reduced viscosity (measured at 30 ° C. using chloroform solvent) 0.40 dl / g of poly (2,6-dimethyl-1,4-phenylene) ether was used.
PPE2: Reduced viscosity (measured at 30 ° C. using chloroform solvent) 0.31 dl / g of poly (2,6-dimethyl-1,4-phenylene) ether was used.
-Polystyrene (B)-
GPPS1: General purpose polystyrene (trade name: Stylon 660 (registered trademark), manufactured by Dow Chemical Company, USA) was used.
-Glass fiber (C)-
GF1: Glass fiber (trade name: EC10 3MM 910 (registered trademark), manufactured by NSG Vetrotex Co., Ltd.) having an average fiber diameter of 10 μm and a fiber cut length of 3 mm, which was surface-treated with an aminosilane compound, was used.
-Flame retardant (D)-
FR1: Triphenyl phosphate (aromatic phosphate ester flame retardant, trade name: TPP (registered trademark), manufactured by Daihachi Chemical Co., Ltd.) was used.
FR2: Bisphenol A bisdiphenyl phosphate (aromatic phosphate ester flame retardant, trade name: CR-741 (registered trademark), manufactured by Daihachi Chemical Co., Ltd.) was used.
FR3: Phosphononitrile acid phenyl ester (phosphazene flame retardant, trade name: Ravitor (registered trademark) FP-110, manufactured by Fushimi Pharmaceutical Co., Ltd.) was used.
-Other materials-
Mica: Trade name: C-1001F (registered trademark), manufactured by Repco Co., Ltd. was used.
Phosphinic acid metal salt flame retardant: Trade name: Exolit OP930 (registered trademark), manufactured by Clariant Japan Co., Ltd. was used.

[Method for measuring physical properties]
(1) Tensile strength The resin composition pellets produced by the following examples and comparative examples were dried in a hot air dryer at 90 ° C. for 1 hour. Using the resin composition after drying, the cylinder temperature was 300 ° C., the mold temperature was 90 ° C., and the injection pressure was 50 MPa (gauge) using an injection molding machine (IS-80EPN, manufactured by Toshiba Machine Co., Ltd.) equipped with an ISO physical property test piece mold. Pressure), injection speed 200 mm / sec, injection time / cooling time = 20 sec / 20 sec, and ISO 3167, a multi-purpose test piece A-type dumbbell molded piece was molded. Using this multipurpose test piece A-type dumbbell molded piece, the tensile strength was measured at 23 ° C. in accordance with ISO 527. As an evaluation standard, it was determined that the higher the measured value, the better the mechanical properties. In particular, when the measured value was 130 MPa or more, it was determined that the resin composition of this embodiment was desirable.
(2) Bending strength ISO 3167 manufactured in the above (1) and multipurpose test piece A-type dumbbell molded piece were cut to form a molded piece of 80 mm × 10 mm × 4 mm. Using the test piece, the bending strength was measured at 23 ° C. in accordance with ISO178. As an evaluation standard, it was determined that the higher the measured value, the better the mechanical properties, and in particular, when the measured value was 170 MPa or more, it was determined that the resin composition of this embodiment was desirable.
(3) Charpy impact strength ISO 3167 manufactured in the above (1), multi-purpose test piece A type dumbbell molded piece was cut to form a molded piece of 80 mm x 10 mm x 4 mm. The Charpy impact strength was measured at 23 ° C. according to ISO 179 using the test piece. As an evaluation standard, it was determined that the higher the measured value, the better the impact resistance.
(4) Thin-flame flame retardancy Using a 0.8 mm-thick Tanzaku molded piece, measurement was performed based on the UL-94 test method to determine the flame retardance level. In particular, in the case of flame retardant level V-0 determination, it was determined that the resin composition of this embodiment is desirable.
(5) Molding fluidity (MFR)
The pellets of the resin composition produced according to the following examples and comparative examples were dried in a hot air dryer at 90 ° C. for 1 hour. After drying, MFR (melt flow rate) was measured using a melt indexer (P-111, manufactured by Toyo Seiki Seisakusho) at a cylinder set temperature of 250 ° C. and a load of 10 kg. As an evaluation standard, the higher the measured value, the better the molding fluidity.
(6) Deflection temperature under load (DTUL)
The ISO 3167 and multipurpose test piece A-type dumbbell molded piece produced in the above (1) was cut to produce a molded piece of 80 mm × 10 mm × 4 mm. Using this test piece, the deflection temperature under load (DTUL) was measured in accordance with ISO75 under the flatwise method at 1.82 MPa. As an evaluation standard, it was determined that the higher the DTUL, the better the heat resistance.
(7) High-temperature tensile strength The tensile strength was measured at 110 ° C. according to ISO 527 using the ISO 3167 manufactured in the above (1) and the multipurpose test piece A-type dumbbell molded piece. As an evaluation standard, it was determined that the higher the measured value, the better the high-temperature durability. In particular, when the measured value was 60 MPa or more, it was determined that the resin composition of the present embodiment was desirable.

Hereinafter, each example and each comparative example will be described in detail.
[Example 1]
34 parts by mass of (PPE1) and a blend obtained by stirring and mixing with a Henschel mixer in advance (FR1) / (PPE1) = 1/3 (rotation speed 600 rpm, stirring time 1 min, internal temperature 23-25 ° C.) 36 parts by weight of ZSK40MC twin-screw extruder manufactured by Werner & Pfleiderer, Germany, number of barrels 13, screw diameter 40mm (kneading disk L: 2, kneading disk R: 6, kneading disk N: 4 The screw pattern is fed from the most upstream part (top feed), 30 parts by weight of (GF1) is fed from the middle barrel 8 and melted at a cylinder temperature of 300 ° C., a screw rotation speed of 250 rpm, and an extrusion rate of 100 kg / h. The resin composition was obtained by kneading. Table 1 shows the physical property test results of the resin composition.

[Example 2]
25 parts by mass of (PPE1) and a blend obtained by stirring and mixing with a Henschel mixer in advance at a ratio of (FR1) / (PPE1) = 1/2 (rotation speed 600 rpm, stirring time 1 min, internal temperature 23-27 ° C.) 45 parts by mass is supplied from the most upstream part (top feed) of the same ZSK40MC twin screw extruder as in Example 1, and 30 parts by mass of (GF1) is side-fed from the middle barrel 8 to a cylinder temperature of 300 ° C., The resin composition was obtained by melt-kneading at a screw rotation speed of 250 rpm and an extrusion rate of 100 kg / h. Table 1 shows the physical property test results of the resin composition.

[Example 3]
(PPE2) 25 parts by mass and (FR1) / (PPE2) = 1/1 ratio previously obtained by stirring and mixing with a Henschel mixer (rotation speed 500 rpm, stirring time 1.5 min, internal temperature 27-30 ° C.) 30 parts by mass of the blend is supplied from the uppermost stream part (top feed) of the same ZSK40MC twin-screw extruder as in Example 1, and 45 parts by mass of (GF1) is side-fed from the middle barrel 8 to obtain a cylinder temperature of 300 The resin composition was obtained by melt-kneading at a temperature of 250 ° C., a screw rotation speed of 250 rpm, and an extrusion rate of 100 kg / h. Table 1 shows the physical property test results of the resin composition.

[Example 4]
(PPE1) 22 parts by mass and a blend obtained by stirring and mixing with a Henschel mixer in advance at a ratio of (FR1) / (PPE1) = 1/2 (rotation speed 600 rpm, stirring time 1 min, internal temperature 23-27 ° C.) 45 parts by mass and 3 parts by mass of (GPPS1) are supplied from the uppermost stream part (top feed) of the same ZSK40MC twin screw extruder as in Example 1, and 30 parts by mass of (GF1) is side-fed from the middle barrel 8 Then, it was melt kneaded at a cylinder temperature of 300 ° C., a screw rotation speed of 250 rpm, and an extrusion rate of 100 kg / h to obtain a resin composition. Table 1 shows the physical property test results of the resin composition.

[Example 5]
56 parts by mass of (PPE1) and 14 parts by mass of (FR3) are supplied from the most upstream part (top feed) of the same ZSK40MC twin screw extruder as in Example 1, and 30 parts by mass of (GF1) from the middle barrel 8 Was fed and melt kneaded at a cylinder temperature of 300 ° C., a screw rotation speed of 250 rpm, and an extrusion rate of 100 kg / h to obtain a resin composition. Table 1 shows the physical property test results of the resin composition.

[Example 6]
56 parts by mass of (PPE1), 10.5 parts by mass of (FR3), and 3.5 parts by mass of (FR2) are supplied from the most upstream part (top feed) of the same ZSK40MC twin screw extruder as in Example 1. Then, 30 parts by mass of (GF1) was fed from the middle barrel 8 and melt-kneaded at a cylinder temperature of 300 ° C., a screw rotation speed of 250 rpm, and an extrusion rate of 100 kg / h to obtain a resin composition. Table 1 shows the physical property test results of the resin composition.

[Comparative Example 1]
(PPE1) 18 parts by mass and blend ratio 45 obtained by stirring and mixing with a Henschel mixer in advance at a ratio of (FR1) / (PPE1) = 1/2 (rotation speed 600 rpm, stirring time 1 min, internal temperature 23-27). Mass part and 7 parts by mass of (GPPS1) are supplied from the uppermost stream part (top feed) of the same ZSK40MC twin screw extruder as in Example 1, and 30 parts by mass of (GF1) are side-fed from the middle barrel 8 The resin composition was obtained by melt kneading at a cylinder temperature of 300 ° C., a screw rotation speed of 250 rpm, and an extrusion rate of 100 kg / h. Table 1 shows the physical property test results of the resin composition.

[Comparative Example 2]
(PPE1) 52 parts by mass is supplied from the most upstream part (top feed) of the same ZSK40MC twin screw extruder as in Example 1, 18 parts by mass of (FR2) is liquidated from the middle barrel 4, and further halfway barrel 8 to 30 parts by weight of (GF1) were side-fed and melt-kneaded at a cylinder temperature of 300 ° C., a screw rotation speed of 250 rpm, and an extrusion rate of 100 kg / h to obtain a resin composition. Table 1 shows the physical property test results of the resin composition.

[Comparative Example 3]
56 parts by mass of (PPE1), 7 parts by mass of (FR3), and 7 parts by mass of (FR2) are supplied from the most upstream part (top feed) of the same ZSK40MC twin screw extruder as in Example 1, and the barrel in the middle 8 to 30 parts by weight of (GF1) were side-fed and melt-kneaded at a cylinder temperature of 300 ° C., a screw speed of 250 rpm, and an extrusion rate of 100 kg / h to obtain a resin composition. Table 1 shows the physical property test results of the resin composition.

[Comparative Example 4]
51 parts by mass of (PPE1) and 4 parts by mass of a phosphinic acid metal salt-based flame retardant (trade name: Exolit OP930, manufactured by Clariant Japan Co., Ltd.), the uppermost stream part (top feed) of the same ZSK40MC twin screw extruder as in Example 1 ), 15 parts by mass of (FR2) is liquid-added from the middle barrel 4, and 30 parts by mass of (GF1) is further side-fed from the middle barrel 8, and the cylinder temperature is 300 ° C. and the screw rotation speed is 250 rpm. The resin composition was obtained by melt-kneading at a rate of 100 kg / h. Table 1 shows the physical property test results of the resin composition.

[Comparative Example 5]
(PPE1) 50 parts by mass, (FR1) 10 parts by mass, mica (trade name: C-1001F [registered trademark], manufactured by Repco) 30 parts by mass of the same ZSK40MC twin screw extruder as in Example 1 Supply from the most upstream part (top feed), side feed 10 parts of (GF1) from the middle barrel 8 and melt knead at a cylinder temperature of 300 ° C., a screw rotation speed of 250 rpm, and an extrusion rate of 100 kg / h. I got a thing. Table 1 shows the physical property test results of the resin composition.

[Comparative Example 6]
35 parts by mass of (PPE2) and 10 parts by mass of (FR1) are supplied from the most upstream part (top feed) of the same ZSK40MC twin screw extruder as in Example 1, and 55 parts by mass of (GF1) from the middle barrel 8 Was fed and melt kneaded at a cylinder temperature of 300 ° C., a screw rotation speed of 250 rpm, and an extrusion rate of 100 kg / h to obtain a resin composition. Table 1 shows the physical property test results of the resin composition.

From the results shown in Table 1, the resin compositions of Examples 1 to 6 had a tensile strength of 130 MPa or more, an excellent flame retardancy level of V-0, and other physical properties were also good. In particular, in the resin composition of Example 1, the above physical properties are further improved by defining the component (D) as triphenyl phosphate and defining the content in the composition. Moreover, in the resin composition of Example 5, the said physical property is further improved by making (D) component into phosphazene. Furthermore, in the resin composition of Example 6, the component (D) is a mixture of an aromatic phosphate ester and phosphazene, and the physical properties are further improved by defining the content of the phosphazene in the component (D). Has been.
On the other hand, in Comparative Examples 1 to 6, such physical properties were not obtained. In Comparative Example 1 in which the content of the component (B) exceeds the range described in claim 1, the tensile strength and the flame retardance level were inferior to those of the Examples. In Comparative Examples 2 to 4, the content of one or more compounds selected from the group consisting of triphenyl phosphate and phosphazene does not satisfy the provisions of claim 1, and the desired effect of the present application is not obtained. . Specifically, the flame retardancy level in Comparative Example 2, the flame retardance level in Comparative Example 3, and the tensile strength in Comparative Example 4 were inferior to those in Examples. In Comparative Example 5 in which the content of the component (C) is lower than the range described in claim 1, the mechanical properties were inferior to those of the Examples. In Comparative Example 6 in which the content of the component (C) exceeds the range described in claim 1, the flame retardancy level was inferior to that of the Examples.

  According to the polyphenylene ether resin composition of the present invention, it is possible to provide a polyphenylene ether resin composition having excellent mechanical properties such as tensile strength, bending strength, impact strength, flame retardancy, and molding fluidity. This polyphenylene ether-based resin composition can be effectively used particularly as a thin molded article such as a cooling fan of an electric / electronic device. Moreover, according to the molded object of this invention, the effect of the said polyphenylene ether-type resin composition of this invention can be acquired. Furthermore, according to the method for producing a polyphenylene ether resin composition of the present invention, the polyphenylene ether resin composition of the present invention can be produced.

Claims (11)

A polyphenylene ether resin composition in which the total mass of polyphenylene ether (A), styrene resin (B), glass fiber (C), and organophosphorus flame retardant (D) is 90% by mass or more,
When the total mass is 100% by mass, polyphenylene ether (A) 25-75% by mass, styrene resin (B) 0-5% by mass, glass fiber (C) 20-50% by mass, and organophosphorous flame retardant ( D) containing 5 to 20% by mass,
Polyphenylene ether resin characterized by containing 70% by mass or more of one or more compounds selected from the group consisting of triphenyl phosphate and phosphazene, with the mass of organophosphorus flame retardant (D) being 100% by mass Composition.   The polyphenylene ether resin composition according to claim 1, wherein the tensile strength (based on ISO 527, measured at 23 ° C.) is 130 MPa or more.   The polyphenylene ether-based resin composition according to claim 1 or 2, wherein the flame retardancy level (conforms to UL94. Conducted with a test piece having a thickness of 0.8 mm) is V-0.   The polyphenylene ether-based resin composition according to any one of claims 1 to 3, wherein the flexural strength (based on ISO 178, measured at 23 ° C) is 170 MPa or more.   The polyphenylene ether-based resin composition according to any one of claims 1 to 4, wherein the high-temperature tensile strength (based on ISO 527, measured at 110 ° C) is 70 MPa or more. The organophosphorus flame retardant (D) is a mixture of an aromatic phosphate ester and a phosphazene, and the organophosphorus flame retardant (D) has a mass of 100% by mass and contains 70 to 95% by mass of phosphazene. The polyphenylene ether-based resin composition according to any one of claims 1 to 5. The said organophosphorus flame retardant (D) is a triphenyl phosphate, The said total mass is 100 mass%, 5-13 mass% of triphenyl phosphate is contained, The any one of Claims 1-5. A polyphenylene ether resin composition. The polyphenylene ether resin composition according to any one of claims 1 to 5 , wherein the organic phosphorus flame retardant (D) is phosphazene.   The polyphenylene ether resin composition according to any one of claims 1 to 8, which does not contain the styrene resin (B). Blending the organophosphorus flame retardant (D) and the polyphenylene ether (A) in a ratio of (D) / (A) = 1/1 to 1/7 to obtain a blend, and The manufacturing method of the polyphenylene ether-type resin composition of any one of Claims 1-9 including the process of knead | mixing this blend and glass fiber (C).   A cooling fan for an electric / electronic device, comprising the polyphenylene ether-based resin composition according to claim 1.