JP7062546B2 - Polyphenylene ether-based resin composition, molded product, and method for improving variation in burning time - Google Patents

Description

The present invention relates to a polyphenylene ether-based resin composition and a molded product, and a method for improving variations in burning time.

The polyphenylene ether-based resin is usually a combination of polyphenylene ether and a styrene-based resin in an arbitrary ratio according to the required heat resistance and molding fluidity level, and further, if necessary, an elastomer component and an elastomer component, etc. A resin composition is obtained by blending additive components such as flame retardants, inorganic fillers, and heat stabilizers. Polyphenylene ether-based resins are widely used in the fields of home appliances OA, office machines, information equipment, automobiles, etc. because they are excellent in heat resistance, mechanical properties, molding processability, acid alkali resistance, dimensional stability, electrical characteristics, and the like. Among these applications, in recent years, extremely high heat resistance, bending strength, and tensile strength as thin-walled molded bodies, such as home appliance OA, cooling fan (propeller) applications for electrical and electronic equipment such as office machines and information equipment such as PCs. Some of them require mechanical properties such as strength, and many of them require durability to withstand long-term stress under high temperature conditions. Fibrous inorganic fillers, especially glass fibers, are used. A polyphenylene ether-based resin composition blended in a large amount has been studied.

On the other hand, in recent years, extremely high flame retardant levels, which have never been seen before, are often required for such applications. It is known that flame retardancy can be achieved to some extent by doing so (see, for example, Patent Documents 1 and 2).

Further, a technique for improving the flame retardancy of a thin-walled molded product in a resin composition in which a large amount of glass fiber is blended with a polyphenylene ether-based resin has already been disclosed (see, for example, Patent Document 3).

Japanese Unexamined Patent Publication No. 8-183902 Japanese Unexamined Patent Publication No. 10-168260 JP-A-2015-209518

However, conventionally, since the resin composition containing the fibrous inorganic filler has combustion sustainability due to the wicking effect, it is extremely difficult to make the flame retardant to a high level even if the flame retardant is added. In particular, when a combustion test conforming to UL94 is performed with a thin-walled test piece having a thickness of 2.0 to 0.5 mm, the combustion time varies widely between the test pieces and the required flame retardant level cannot be cleared. Therefore, even if the techniques disclosed in Patent Documents 1 and 2 are used, sufficient flame retardancy may not always be obtained.
Further, although Patent Document 3 shows that the flame retardancy of the thin-walled molded product is remarkably improved, the improvement of the variation in the burning time between the test pieces is not sufficiently made. In addition, since the flame retardant is limited to a solid flame retardant having a low melting point such as triphenyl phosphate, it may be difficult to handle, and due to the generation of mold MD (mold deposit) during molding. In some cases, the frequency of mold cleaning increases, the work becomes complicated, and the molding work environment deteriorates due to the generation of a large amount of gas, which is not always sufficient.

Therefore, the present invention is a polyphenylene ether-based resin containing glass fiber, which has excellent heat resistance, mechanical characteristics, and handleability, and can be effectively used even in a usage environment where long-term durability is required. It is an object of the present invention to provide a method for improving the variation of the composition, the molded product thereof, and the burning time thereof.

As a result of diligent studies to solve the above problems, the present inventors have blended a specific type of condensed phosphoric acid ester flame retardant in a polyphenylene ether-based resin composition containing 11 to 50% by mass of glass fiber. It has been found that a resin composition having excellent heat resistance, mechanical properties, and handleability can be obtained by making it flame retardant, and the present invention has been provided.

（式中、Ｒ^１～Ｒ^４は、２，６－キシリル基であり、ｎは１～３である。）
［２］
前記（Ａ）、（Ｂ）、（Ｃ）、及び（Ｄ）成分の合計含有量が、前記ポリフェニレンエーテル系樹脂組成物全体の９０質量％以上を占める、［１］に記載のポリフェニレンエーテル系樹脂組成物。
［３］
前記（Ａ）成分の一部又は全部が、カルボン酸又は酸無水物で官能化された官能化ポリフェニレンエーテルである、［１］又は［２］に記載のポリフェニレンエーテル系樹脂組成物。
［４］
ＵＬ９４に準拠して、厚み０．７ｍｍの試験片で燃焼試験を実施したときの難燃レベルがＶ－０である、［１］～［３］のいずれかに記載のポリフェニレンエーテル系樹脂組成物。
［５］
前記垂直燃焼試験を実施したとき、最大燃焼秒数と最小燃焼秒数との差が５．０秒以内である、［４］に記載のポリフェニレンエーテル系樹脂組成物。
［６］
［１］～［５］のいずれかに記載のポリフェニレンエーテル系樹脂組成物を含むことを特徴とする、成形体。
［７］
厚みが０．５～２．０ｍｍであり、ＵＬ９４に準拠して垂直燃焼試験を実施したときの難燃レベルがＶ－０である、［６］に記載の成形体。
［８］
電気・電子機器の冷却ファンである、［６］又は［７］に記載の成形体。
［９］
ポリフェニレンエーテル（Ａ）、スチレン系樹脂（Ｂ）、難燃剤（Ｃ）、及びガラス繊維（Ｄ）を含有し、前記（Ａ）、（Ｂ）、（Ｃ）、及び（Ｄ）成分の合計量１００質量％に対する各成分の含有量が、（Ａ）成分２０～８４質量％、（Ｂ）成分０～５質量％、（Ｃ）成分５～２５質量％、（Ｄ）成分１１～５０質量％であるポリフェニレンエーテル系樹脂組成物において、ＵＬ９４に準拠して、厚み０．７ｍｍの試験片で垂直燃焼試験を実施したときの燃焼時間のバラツキ（最小燃焼秒数と最大燃焼秒数との差）を改善する方法であり、
前記難燃剤（Ｃ）として、前記（Ｃ）成分１００質量％に対して、ビスフェノールＡビスジフェニルホスフェート（Ｃ－１）５０～９５質量％及び下記化学式（１）で表される縮合型リン酸エステル系難燃剤（Ｃ－２）５０～５質量％を含む混合物を用いることを特徴とする、方法。

（式中、Ｒ^１～Ｒ^４は、２，６－キシリル基であり、ｎは１～３である。） That is, the present invention is as follows.
[1]
Contains polyphenylene ether (A), styrene resin (B), flame retardant (C), and glass fiber (D), and the total amount of the components (A), (B), (C), and (D). The content of each component with respect to 100% by mass is (A) component 20 to 84% by mass, (B) component 0 to 5% by mass, (C) component 5 to 25% by mass, and (D) component 11 to 50% by mass. The component (C) is 50 to 95 % by mass of bisphenol A bisdiphenyl phosphate (C-1) and condensed phosphorus represented by the following chemical formula (1) with respect to 100% by mass of the component (C). A polyphenylene ether-based resin composition, which is a mixture containing 50 to 5 % by mass of an acid ester-based flame retardant (C-2).

(In the formula, R ¹ to R ⁴ are 2,6-kisilyl groups, and n is 1 to 3).
[2]
The polyphenylene ether-based resin according to [1], wherein the total content of the components (A), (B), (C), and (D) accounts for 90% by mass or more of the entire polyphenylene ether-based resin composition. Composition.
[3]
The polyphenylene ether-based resin composition according to [1] or [2], wherein a part or all of the component (A) is a functionalized polyphenylene ether functionalized with a carboxylic acid or an acid anhydride.
[4 ]
The polyphenylene ether-based resin composition according to any one of [1] to [ 3 ], wherein the flame retardant level is V-0 when a combustion test is carried out with a test piece having a thickness of 0.7 mm in accordance with UL94 . thing.
[ 5 ]
The polyphenylene ether-based resin composition according to [ 4 ], wherein the difference between the maximum combustion seconds and the minimum combustion seconds is within 5.0 seconds when the vertical combustion test is carried out.
[ 6 ]
A molded product comprising the polyphenylene ether-based resin composition according to any one of [1] to [ 5 ].
[ 7 ]
The molded product according to [ 6 ], which has a thickness of 0.5 to 2.0 mm and has a flame retardancy level of V-0 when a vertical combustion test is carried out in accordance with UL94.
[ 8 ]
The molded product according to [ 6 ] or [ 7 ], which is a cooling fan for electrical / electronic equipment.
[ 9 ]
Contains polyphenylene ether (A), styrene resin (B), flame retardant (C), and glass fiber (D), and the total amount of the components (A), (B), (C), and (D). The content of each component with respect to 100% by mass is (A) component 20 to 84% by mass, (B) component 0 to 5% by mass, (C) component 5 to 25% by mass, and (D) component 11 to 50% by mass. In the polyphenylene ether-based resin composition, which is based on UL94, the variation in combustion time when a vertical combustion test is performed on a test piece having a thickness of 0.7 mm (difference between the minimum combustion seconds and the maximum combustion seconds). Is a way to improve
As the flame retardant (C), bisphenol A bisdiphenyl phosphate (C-1) 50 to 95 % by mass and a condensed phosphoric acid ester represented by the following chemical formula (1) with respect to 100% by mass of the component (C). A method comprising the use of a mixture containing 50-5 % by mass of the flame retardant (C-2).

(In the formula, R ¹ to R ⁴ are 2,6-kisilyl groups, and n is 1 to 3).

According to the present invention, a polyphenylene ether-based resin containing glass fiber, which has excellent heat resistance, mechanical properties, and handleability, can be effectively used even in a usage environment where long-term durability is required. It is possible to provide a method for improving the variation of the composition, the molded product thereof, and the burning time thereof.

Hereinafter, embodiments 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 can be variously modified and carried out within the scope of the gist thereof.

（式中、Ｒ¹～Ｒ⁴は、２，６－キシリル基であり、ｎは１～３である。） [Resin composition]
The polyphenylene ether-based resin composition of the present embodiment contains the polyphenylene ether (A), the styrene-based resin (B), the flame retardant (C), and the glass fiber (D), and the above-mentioned (A), (B), and the like. The content of each component with respect to the total amount of 100% by mass of the components (C) and (D) is 20 to 84% by mass of the component (A), 0 to 5% by mass of the component (B), and 5 to 25 by the component (C). The mass% is 11 to 50% by mass of the component (D), and the component (C) is 0 to 97% by mass of bisphenol A bisdiphenyl phosphate with respect to 100% by mass of the component (C). It is characterized by containing 100 to 3% by mass of a condensed phosphoric acid ester flame retardant (C-2) represented by the following chemical formula (1).

(In the formula, R ¹ to R ⁴ are 2,6-kisilyl groups, and n is 1 to 3).

但し、上記化学式（２）及び（３）中、Ｒ_３、Ｒ_４、Ｒ_５、Ｒ_６、Ｒ_７、及びＲ_８は、それぞれ独立して、水素原子、炭素数１～４のアルキル基、炭素数６～９のアリール基、又はハロゲン原子を表す。但し、Ｒ_７及びＲ_８は同時に水素原子ではない。
また、前記アルキル基の好ましい炭素数は１～３であり、前記アリール基の好ましい炭素数は６～８であり、前記一価の残基の中でも水素原子が好ましい。
尚、上記化学式（２）、（３）で表される繰り返し単位の数については、ポリフェニレンエーテル（Ａ）の分子量分布により様々であるため、特に制限されることはない。 (Polyphenylene ether (A))
The polyphenylene ether (A) of the present embodiment (hereinafter, the polyphenylene ether is also simply referred to as “PPE”) will be described.
The polyphenylene ether (A) of the present embodiment is a homopolymer or a copolymer having a repeating unit (structure unit) represented by the following chemical formulas (2) and / or chemical formulas (3). Is preferable.

However, in the above chemical formulas (2) and (3), R ₃ , R ₄ , R ₅ , R ₆ , R ₇ and R ₈ are independently hydrogen atoms and alkyl groups having 1 to 4 carbon atoms, respectively. Represents an aryl group having 6 to 9 carbon atoms or a halogen atom. However, R ₇ and R ₈ are not hydrogen atoms at the same time.
The alkyl group preferably has 1 to 3 carbon atoms, the aryl group preferably has 6 to 8 carbon atoms, and a hydrogen atom is preferable among the monovalent residues.
The number of repeating units represented by the above chemical formulas (2) and (3) is not particularly limited because it varies depending on the molecular weight distribution of the polyphenylene ether (A).

Typical examples of homopolymers of polyphenylene ether are poly (2,6-dimethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, and 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-) Examples thereof include 1,4-phenylene) ether, poly (2-methyl-6-hydroxyethyl-1,4-phenylene) ether, and poly (2-methyl-6-chloroethyl-1,4-phenylene) ether.

The copolymer of polyphenylene ether is not limited to the following, and is, for example, a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, and 2,6-dimethylphenol and o. -Mainly repeating units having a polyphenylene ether structure represented by the chemical formula (2) and / or the chemical formula (3), such as a copolymer with cresol and a copolymer of 2,3,6-trimethylphenol and o-cresol. And so on. Among the polyphenylene ethers, poly (2,6-dimethyl-1,4-phenylene) ethers are preferable.

In the polyphenylene ether (A), the terminal OH group concentration is 0.4 to 2.0 per 100 monomer units constituting the polyphenylene ether from the viewpoint of sufficient adhesion to the glass fiber as the component (D). The number is preferably 0.6 to 1.3, more preferably 0.6 to 1.3.
The terminal OH group concentration of PPE can be calculated by NMR measurement.

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

In the present embodiment, at least a part of the polyphenylene ether chain has a structure in which R ₃ and R ₄ are methyl groups in the chemical formula (2) (and a structure derived from the structure as described later). It is preferable that it is contained.

The polyphenylene ether (A) contains polyphenylene ether containing various phenylene ether units other than the above chemical formulas (2) and (3) as a partial structure as long as the heat resistance of the resin composition is not excessively lowered. You may be.
The various phenylene ether units other than the above chemical formulas (2) and (3) are not limited to the following, and are, for example, in JP-A No. 01-297428 and JP-A-63-301222. Examples thereof include 2- (dialkylaminomethyl) -6-methylphenylene ether unit and 2- (N-alkyl-N-phenylaminomethyl) -6-methylphenylene ether unit described.
In the polyphenylene ether (A), a small amount of repeating units derived from diphenoquinone or the like may be bonded to the main chain of the polyphenylene ether.

Further, in the polyphenylene ether (A), a part or all of the constituent units constituting the polyphenylene ether are a carboxyl group, an acid anhydride group, an acid amide group, an imide group, an amine group, an orthoester group, a hydroxy group, and a carboxylic acid. It is preferable to have a configuration in which the functionalized polyphenylene ether is replaced by reacting (modifying) with a functionalizing agent containing one or more functional groups selected from the group consisting of groups derived from ammonium salts.
In particular, from the viewpoint of improving adhesion to glass fiber, which is a component of the present application (D), and improving heat resistance, mechanical properties, etc., polyphenylene ether is an acid anhydride such as maleic anhydride, malic acid, citric acid, and fumaric acid. The functionalized polyphenylene ether functionalized by reacting with carboxylic acids such as the above is preferably a part or all of the polyphenylene ether (A), and more preferably maleic anhydride obtained by reacting the polyphenylene ether with maleic anhydride. It is an acid-modified polyphenylene ether. For the maleic anhydride-modified polyphenylene ether, for example, 2 to 5 parts by mass of maleic anhydride is mixed with 100 parts by mass of the polyphenylene ether with a tumbler mixer and charged into a twin-screw extruder at a temperature of 270 to 335 ° C. It can be obtained by melt-kneading.

In the polyphenylene ether (A), from the viewpoint of further improving the adhesion to the glass fiber as the component (D), the concentration of the functionalized modified terminal is 0. The number is preferably 1 to 10, more preferably 0.1 to 3.0, and even more preferably 0.1 to 1.0.
The modified terminal concentration of PPE can be calculated by NMR measurement.

The ratio (Mw / Mn value) of the weight average molecular weight Mw of the polyphenylene ether (A) to the number average molecular weight Mn is preferably 2.0 to 5.5, more preferably 2.5 to 4.5, and further. It is preferably 3.0 to 4.5.
The Mw / Mn value is preferably 2.0 or more from the viewpoint of molding processability of the resin composition, and preferably 5.5 or less from the viewpoint of the mechanical physical properties of the resin composition.
The number average molecular weight Mn of the polyphenylene ether (A) is preferably 8000 to 28000, more preferably 12000 to 24000, and further preferably 14000 to 22000 from the viewpoint of molding processability and mechanical characteristics.
Here, the weight average molecular weight Mw and the number average molecular weight Mn are obtained from polystyrene-equivalent molecular weights measured by GPC (gel permeation chromatography).

The reducing viscosity of the polyphenylene ether (A) is preferably in the range of 0.25 to 0.65 dL / g. It is more preferably in the range of 0.30 to 0.55 dL / g, and even more preferably in the range of 0.33 to 0.42 dL / g.
The reducing viscosity of the polyphenylene ether (A) is preferably 0.25 dL / g or more from the viewpoint of sufficient mechanical characteristics, and preferably 0.65 dL / g or less from the viewpoint of molding processability.
The reduced viscosity can be measured using a Ubbelohde viscometer at 0.5 g / dL chloroform solution at 30 ° C.

The polyphenylene ether (A) is generally available as a powder, and its preferred particle size is an average particle diameter of 1 to 1000 μm, more preferably 10 to 700 μm, and particularly preferably 100 to 500 μm. From the viewpoint of handleability during processing, 1 μm or more is preferable, and 1000 μm or less is preferable in order to suppress the generation of unmelted matter during melt-kneading.

In the resin composition of the present embodiment, the polyphenylene ether (A) in a total amount of 100% by mass of the polyphenylene ether (A), the styrene resin (B), the flame retardant (C), and the glass fiber (D). ) Is in the range of 20 to 84% by mass. It is preferably in the range of 35 to 60% by mass, more preferably 40 to 55% by mass.
The content of the polyphenylene ether (A) is preferably 20% by mass or more from the viewpoint of imparting sufficient heat resistance and flame retardancy, and is preferably 84% by mass or less from the viewpoint of molding processability.

(Styrene resin (B))
In the resin composition of the present embodiment, the styrene-based resin (B) is obtained by polymerizing a styrene-based compound or a styrene-based compound and a compound copolymerizable with the styrene-based compound in the presence or absence of a rubbery polymer. It is a polymer obtained by the above.
As the styrene resin (B), only one type may be used alone, or two or more types may be mixed and used.

The styrene-based compound is not limited to the following, and is, for example, styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, p-methylstyrene, p-tert-butylstyrene, ethylstyrene. And so on. In particular, styrene is preferable from the viewpoint of practicality of raw materials.

The compound that can be copolymerized with the styrene-based compound is not limited to the following, and is, for example, methacrylic anhydrides such as methyl methacrylate and ethyl methacrylate; and unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile; Examples thereof include acid anhydrides such as maleic anhydride.
The amount of the compound copolymerizable with the styrene compound is preferably 30% by mass or less, preferably 15% by mass or less, based on 100% by mass of the total amount of the styrene compound and the compound copolymerizable with the styrene compound. More preferred.

Further, the rubbery polymer is not limited to the following, and examples thereof include a conjugated diene-based rubber, a copolymer of a conjugated diene and an aromatic vinyl compound, and an ethylene-propylene copolymer-based rubber, and more specifically. , Polybutadiene, styrene-butadiene random copolymers and styrene-butadiene block copolymers, and polymers in which these are partially or almost completely hydrogenated.

Here, among the above-mentioned styrene-based resins, the polymer or copolymer obtained by polymerizing or copolymerizing in the presence of a rubbery polymer is referred to as a rubber-reinforced styrene-based resin, and is not a rubbery polymer. A polymer or copolymer obtained by polymerizing or copolymerizing in the presence is referred to as a styrene-based resin which is not rubber-reinforced.
As the styrene-based resin (B), a styrene-based resin that is not rubber-reinforced, such as general purpose polystyrene (GPPS), is preferable from the viewpoint of mechanical properties of the molded body.

In the resin composition of the present embodiment, the styrene-based resin (in 100% by mass) of the total amount of the polyphenylene ether (A), the styrene-based resin (B), the flame retardant (C), and the glass fiber (D). The content of B) is in the range of 0 to 5% by mass. It is preferably in the range of 0 to 3% by mass.
The styrene-based resin (B) is preferably added from the viewpoint of improving the molding fluidity of the resin composition of the present embodiment, but is blended in an amount of 5% by mass or less from the viewpoint of imparting sufficient mechanical properties and flame retardancy. It is desirable to have.

上記化学式（１）の、Ｒ¹～Ｒ⁴は、２，６－キシリル基であり、ｎは１～３から選ばれる。ｎは１又は２が好ましく、ｎは１がより好ましい。
難燃剤（Ｃ）として、（Ｃ）成分１００質量％に対して（Ｃ－１）０～９７質量％及び（Ｃ－２）１００～３質量％を含む混合物を用いることにより、後述の垂直燃焼試験（ＵＬ９４に準拠）を実施したときの試験片間における燃焼時間のバラツキを改善することができる。 (Flame retardant (C))
The flame retardant (C) used in the resin composition of the present embodiment is bisphenol A bisdiphenyl phosphate (C-1) 0 with respect to 100% by mass of the component (C) from the viewpoint of reducing environmental load and flame retardant performance. It is a flame retardant containing ~ 97% by mass and 100 to 3% by mass of the condensed phosphoric acid ester flame retardant (C-2) represented by the following formula (1).

In the above chemical formula (1), R ¹ to R ⁴ are 2,6-kisilyl groups, and n is selected from 1 to 3. n is preferably 1 or 2, and n is more preferably 1.
By using a mixture containing (C-1) 0 to 97% by mass and (C-2) 100 to 3% by mass with respect to 100% by mass of the component (C) as the flame retardant (C), vertical combustion described later is used. It is possible to improve the variation in the burning time between the test pieces when the test (based on UL94) is carried out.

In the resin composition of the present embodiment, when the flame retardant (C) is used in combination with the above (C-1) and the above (C-2), sufficient flame retardancy is imparted, and vertical combustion described later is performed. It is desirable from the viewpoint of improving the variation in combustion time between test pieces when the test (based on UL94) is carried out, improving the impact strength, and preventing MD adhesion to the mold. The component (C) is 100% by mass, preferably a combination of 97 to 30% by mass of (C-1) and 3 to 70% by mass of (C-2), and more preferably 97 to 70% by mass of (C-1). It is a combination of 50% by mass and (C-2) 3 to 50% by mass, and more preferably a combination of (C-1) 95 to 50% by mass and (C-2) 5 to 50% by mass. Particularly preferably, (C-1) 95 to 70% by mass and (C-2) 5 to 30% by mass are used in combination.

In the resin composition of the present embodiment, the flame retardant (C) in a total amount of 100% by mass of the polyphenylene ether (A), the styrene resin (B), the flame retardant (C), and the glass fiber (D). ) Is in the range of 5 to 25% by mass. It is preferably in the range of 8 to 20% by mass, and more preferably in the range of 10 to 15% by mass.
The flame retardant (C) is preferably contained in an amount of 5% by mass or more from the viewpoint of improving the flame retardancy of the resin composition of the present embodiment, and is contained in an amount of 25% by mass or less from the viewpoint of maintaining sufficient mechanical properties and heat resistance. It is desirable to have.

(Glass fiber (D))
The glass fiber (D) is blended in the resin composition of the present embodiment for the purpose of improving the mechanical strength.

As the type of glass of the glass fiber (D), known ones can be used, and examples thereof include E glass, C glass, S glass, and A glass. The glass fiber (D) refers to fiber-shaped glass and is distinguished from lumpy glass flakes and glass powder.

The average fiber diameter of the glass fiber (D) is preferably 5 to 15 μm, more preferably 7 to 13 μm. From the viewpoint of deterioration of rigidity, heat resistance, impact resistance, durability, etc. of the molded body due to fiber breakage during extrusion and molding, and production stability, 5 μm or more is preferable, and sufficient mechanical properties are imparted and the surface appearance of the molded body is maintained. From the viewpoint, it is preferably 15 μm or less.

The average length of the glass fiber (D) is preferably 0.5 mm or more, more preferably 1 mm or more, and 10 mm from the viewpoint of handleability, from the viewpoint of imparting sufficient rigidity and handleability. It is preferably less than or equal to, and more preferably 6 mm or less.

The glass fiber (D) used in the present embodiment may be surface-treated with a surface treatment agent, for example, a silane compound. The silane compound used as a surface treatment agent is usually used for surface treatment of glass fillers, mineral fillers and the like. Specific examples thereof include vinyl silane compounds such as vinyl trichlorosilane, vinyl triethoxysilane, and γ-methacryloxypropyltrimethoxysilane, epoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane, and bis- (3-triethoxy). Cyrilpropyl) Examples thereof include sulfur-based silane compounds such as tetrasulfide, mercaptosilane compounds such as γ-mercaptopropyltrimethoxysilane, and aminosilane compounds such as γ-aminopropyltriethoxysilane and γ-ureidopropyltriethoxysilane. A particularly preferred silane compound for the purposes of the present invention is an aminosilane compound. These silane compounds may be used alone or in combination of two or more. Further, the surface treatment may be performed with a mixture of these silane compounds and an epoxy-based or urethane-based converging agent in advance.

In the resin composition of the present embodiment, the glass fiber (D) in the total amount of the polyphenylene ether (A), the styrene resin (B), the flame retardant (C), and the glass fiber (D) is 100% by mass. ) Is in the range of 11 to 50% by mass. It is preferably in the range of 15 to 40% by mass, and more preferably in the range of 25 to 35% by mass.
The glass fiber (D) is preferably contained in an amount of 11% by mass or more from the viewpoint of improving the mechanical properties of the resin composition of the present embodiment, and is 50% by mass or less from the viewpoint of maintaining sufficient moldability and imparting flame retardancy. It is desirable that it is contained.

The polyphenylene ether-based resin composition of the present embodiment has the above-mentioned (A), (B), and (C) from the viewpoint of improving heat resistance, mechanical properties, flame retardancy, and surface appearance of the molded product. , And the total content of the component (D) preferably occupies 90% by mass or more of the total polyphenylene ether-based resin composition. The content is more preferably 95% by mass or more, and may be 100% by mass.

(Other materials)
The resin composition of the present embodiment can contain a styrene-based thermoplastic elastomer, a phenol terpene resin, or the like within a range that does not significantly deteriorate the heat resistance, mechanical properties, flame retardancy, and surface appearance of the molded body. be. The content of these components can be in the range of 1 to 5% by mass with respect to 100% by mass of the resin composition. The content is more preferably in the range of 1 to 4% by mass, still more preferably in the range of 1 to 3% by mass. From the viewpoint of exhibiting a sufficient addition effect, the content is preferably 1% by mass or more, and from the viewpoint of maintaining physical properties, the content is preferably 5% by mass or less.

In the resin composition of the present embodiment, stabilizers such as antioxidants, ultraviolet absorbers, and heat stabilizers are used as long as the heat resistance, mechanical properties, flame retardancy, and surface appearance of the molded product are not significantly deteriorated. It is possible to contain a colorant, a mold release agent and the like in the resin composition of the present application in a proportion of 0.001 to 3% by mass. It is preferably in the range of 0.01 to 2% by mass, more preferably in the range of 0.2 to 1% by mass.
From the viewpoint of exhibiting a sufficient addition effect, it is desirable to make it 0.001% by mass or more, and from the viewpoint of maintaining physical properties, it is desirable to make it 3% by mass or less.

In the resin composition of the present embodiment, 0.5 to 10 mass of an inorganic filler other than glass fiber is added to the resin composition of the present application within a range that does not significantly reduce the mechanical properties, impact resistance, and flame retardancy. % Can be contained. It is preferably 1 to 10% by mass, more preferably 2 to 8% by mass. The inorganic filler other than the glass fiber is not limited to the following, and examples thereof include carbon fiber, mica, glass flakes, talc, glass milled fiber, and chlorite.

[Physical characteristics of resin composition]
The flame retardancy level (based on UL-94) of the resin composition of the present embodiment is UL94 with a Tanzaku test piece having a thickness of 0.7 mm from the viewpoint of preventing the spread of fire due to ignition inside the device of the thin-walled molded product. When the vertical combustion test is carried out in accordance with the above, it is preferably V-0. In addition, the number of combustion seconds measured at the time of the first flame contact and the second flame contact (5 x 2 times, a total of 10 flame contact) when the vertical combustion test was performed with 5 test pieces in accordance with UL94. The difference between the minimum number of burning seconds and the maximum number of burning seconds is preferably 5 seconds or less, and more preferably 4 seconds or less.
When the resin composition of the present embodiment is used for a cooling fan of an electric / electronic device, the difference between the minimum combustion seconds and the maximum combustion seconds is preferably within 4 seconds from the viewpoint of stability of flame retardant performance. And more preferably within 3 seconds.
The flame retardancy level, the minimum burning seconds, and the maximum burning seconds of the resin composition can be specifically measured by the methods described in Examples described later.

When the resin composition of the present embodiment is used for a thin-walled molded product, the tensile strength of the resin composition (based on ISO527, measured at 23 ° C.) is 120 MPa or more from the viewpoint of shape retention during use and prevention of cracking. Is preferable. It is more preferably 130 MPa or more, still more preferably 140 MPa or more.
Specifically, the tensile strength of the resin composition can be measured by the method described in Examples described later.

The bending strength of the resin composition of the present embodiment (based on ISO178, measured at 23 ° C.) is preferably 170 MPa or more from the viewpoint of maintaining the shape of the thin-walled molded product during use. It is more preferably 180 MPa or more, and even more preferably 190 MPa or more.
Specifically, the bending strength of the resin composition can be measured by the method described in Examples described later.

The Charpy impact strength (based on ISO179, measured at 23 ° C.) of the resin composition of the present embodiment is preferably 7 kJ / m ² or more from the viewpoint of preventing cracking during high-speed use. More preferably, it is 10 kJ / m ² or more.
The Charpy impact strength of the resin composition can be specifically measured by the method described in Examples described later.

The melt flow rate (MFR) (based on ISO1133, measured at 250 ° C. and a load of 10 kg) of the resin composition of the present embodiment is preferably 3 g / 10 min or more from the viewpoint of moldability of the thin-walled molded product. More preferably, it is 5 g / 10 min or more.
Specifically, the MFR of the resin composition can be measured by the method described in Examples described later.

The deflection temperature under load (DTUL) (based on ISO75, measured under a flatwise method and a 1.82 MPa load) of the resin composition of the present embodiment is 100 ° C. or higher from the viewpoint of durability when the thin-walled molded product is used at a high temperature. It is preferable to have. It is more preferably 125 ° C. or higher, and even more preferably 135 ° C. or higher.
Specifically, the DTUL of the resin composition can be measured by the method described in Examples described later.

[Manufacturing method of 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, if necessary, other materials.
The conditions for producing the resin composition of the present embodiment are not limited to the following, but for example, the components (A), (B), (C), and (D) of the present application are collectively melted. It is also possible to knead to produce the resin composition of the present application. From the viewpoint of improving mechanical properties and achieving sufficient effects of the present application, a functionalized polyphenylene ether component was produced by melt-kneading and reacting the polyphenylene ether (A) with a reactive compound such as a carboxylic acid or an acid anhydride in advance. Later, this is used in place of part or all of the polyphenylene ether (A) before functionalization, and melt-kneaded with the components (B), (C), (D) of the present application, and other components in the next step. It is preferable to produce the resin composition of the present application.
Further, it is sufficient heat resistance and mechanical properties to melt and knead the components (A), (B), and other components first, and then mix and knead the components (C) and (D). It is preferable from the viewpoint of granting.

The method for preparing the resin composition of the present embodiment is not limited to the following, but a twin-screw extruder is preferably used from the viewpoint of production efficiency in order to stably produce a large amount of the resin composition. ..
The screw diameter of the twin-screw extruder is preferably in the range of 25 to 90 mm. More preferably, it is in the range of 40 to 70 mm. For example, ZSK40MC twin-screw extruder (manufactured by German company Werner & Pfreederer, number of barrels 13, screw diameter 40 mm, L / D = 50; kneading disc L: 2, kneading disc R: 6, and kneading disc N: A method of melt-kneading under the conditions of a cylinder temperature of 270 to 330 ° C., a screw rotation speed of 150 to 450 rpm, and an extrusion rate of 40 to 220 kg / h when using a screw pattern having four pieces, or a TEM58SS twin-screw extruder (Toshiba). A screw pattern manufactured by Kikai Co., Ltd., having 13 barrels, a screw diameter of 58 mm, L / D = 53; a kneading disc L: 2, a kneading disc R: 14, and a kneading disc N: 2) was used. In this case, a method of melt-kneading under the 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 can be mentioned as a suitable method.
Here, the "L" is the "screw barrel length" of the extruder, and the "D" is the "screw barrel diameter".
When the resin composition of the present embodiment is produced by using a twin-screw extruder, the component (A), the component (B), and the component (C-2) are obtained from the viewpoint of imparting heat resistance and mechanical properties of the material. Is supplied from the supply port (top feed) at the uppermost stream of the extruder, the component (C-1) is supplied from the supply port (liquid addition nozzle) provided in the middle of the extruder, and the component (D) is supplied from the extruder. It is preferable to supply the material from the raw material push-in supply port (side feed) provided on the way.

[Molded product]
A molded product made of the resin composition of the present embodiment can be obtained by molding the above-mentioned resin composition.

The molded product of the present embodiment is a thin-walled molded product having a thickness of 0.5 to 2.0 mm, and has a flame retardancy level of V-0 when a vertical combustion test is carried out in accordance with UL94. Is preferable. In this case, it is possible to prevent the spread of fire due to ignition inside the apparatus of the thin-walled molded product.

The molding method of the resin composition is not particularly limited, but for example, methods such as injection molding, extrusion molding, vacuum forming, and pressure molding are preferable, and in particular, the appearance characteristics and mass productivity of the molded body are mentioned. From the viewpoint of, injection molding is preferable.

Suitable molded bodies include cooling fans for electrical and electronic devices because they are excellent in heat resistance and mechanical strength, and are also remarkably excellent in thin-walled flame retardancy.

（式中、Ｒ¹～Ｒ⁴は、２，６－キシリル基であり、ｎは１～３である。） [How to improve the variation in burning time]
The method for improving the variation in the burning time of the polyphenylene ether-based resin composition of the present embodiment contains polyphenylene ether (A), a styrene-based resin (B), a flame retardant (C), and a glass fiber (D). The content of each component with respect to the total amount of 100% by mass of the components (A), (B), (C), and (D) is 20 to 84% by mass of the component (A) and 0 to 5% by mass of the component (B). %, (C) component 5 to 25% by mass, (D) component 11 to 50% by mass, a vertical combustion test was carried out with a test piece having a thickness of 0.7 mm in accordance with UL94. It is a method to improve the variation in burning time (difference between the minimum burning seconds and the maximum burning seconds).
As the flame retardant (C), bisphenol A bisdiphenyl phosphate (C-1) 0 to 97% by mass and a condensed phosphoric acid ester represented by the following chemical formula (1) with respect to 100% by mass of the component (C). It is characterized by using a mixture containing 100 to 3% by mass of the flame retardant (C-2).

(In the formula, R ¹ to R ⁴ are 2,6-kisilyl groups, and n is 1 to 3).

In the above polyphenylene ether-based resin composition, a mixture containing (C-1) 0 to 97% by mass and (C-2) 100 to 3% by mass as the flame retardant (C) with respect to 100% by mass of the component (C). By using UL94, it is possible to improve the variation in combustion time (difference between minimum combustion seconds and maximum combustion seconds) when a vertical combustion test is performed with a test piece having a thickness of 0.7 mm. can.
The variation in the burning time (difference between the minimum burning seconds and the maximum burning seconds) of the resin composition can be specifically measured by the method described in Examples described later.

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

The methods and raw materials for measuring physical properties used in Examples , Reference Examples, and Comparative Examples are shown below.

(1. Deflection temperature under load (DTUL))
The pellets of the resin composition produced according to Examples , Reference Examples, and Comparative Examples were dried in a hot air dryer at 90 ° C. for 1 hour.
Using the dried resin composition, an injection molding machine (IS-80EPN, manufactured by Toshiba Machinery Co., Ltd.) equipped with an ISO physical property test piece mold has a cylinder temperature of 300 ° C, a mold temperature of 90 ° C, and an injection pressure of 50 MPa (gauge). Pressure), injection speed 200 mm / sec, injection time / cooling time = 20 sec / 20 sec, ISO3167, multipurpose test piece A type dumbbell molded piece was molded. The obtained multipurpose test piece A type dumbbell molded piece was cut to prepare a test piece having a size of 80 mm × 10 mm × 4 mm. Using the test piece, the deflection temperature under load (DTUL) (° C.) was measured at 1.82 MPa by the flatwise method in accordance with ISO75.
As an evaluation standard, it was determined that the higher the value of DTUL, the better the heat resistance.

(2. Charpy impact strength)
Above 1. ISO3167, multipurpose test piece A type dumbbell molded piece manufactured in the above was cut to prepare a test piece of 80 mm × 10 mm × 4 mm. Using the test piece, the Charpy impact strength (with notch) (kJ / m ² ) was measured at 23 ° C. in accordance with ISO179.
As an evaluation standard, it was judged that the higher the measured value, the better the impact resistance.

(3. Molding fluidity (MFR))
The pellets of the resin composition produced according to Examples , Reference Examples, and Comparative Examples were dried in a hot air dryer at 90 ° C. for 1 hour. After drying, MFR (melt flow rate) (g / 10min) is measured using a melt indexer (P-111, manufactured by Toyo Seiki Seisakusho Co., Ltd.) at a cylinder set temperature of 250 ° C. and a 10 kg load in accordance with ISO1133. bottom.
As an evaluation standard, it was determined that the higher the measured value, the better the molding fluidity.

(4. Tensile strength)
Above 1. The tensile strength (MPa) was measured at 23 ° C. in accordance with ISO527 using the ISO3167 and the multipurpose test piece A type dumbbell molded piece manufactured in.
As an evaluation standard, it was determined that the higher the measured value, the better the mechanical properties, and particularly when the measured value was 130 MPa or more, it was determined that the resin composition of the present embodiment was preferable.

(5. Bending strength)
Above 1. ISO3167, multipurpose test piece A type dumbbell molded piece manufactured in the above was cut to prepare a test piece of 80 mm × 10 mm × 4 mm. Using the test piece, the bending strength (MPa) 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 particularly when the measured value was 170 MPa or more, it was determined that the resin composition of the present embodiment was preferable.

(6. Mold MD evaluation)
The pellets of the resin composition produced according to Examples , Reference Examples, and Comparative Examples were dried in a hot air dryer at 90 ° C. for 1 hour. The dried resin composition is injected at a cylinder temperature of 320 ° C., a mold temperature of 120 ° C., and an injection molding machine (IS-80EPN, manufactured by Toshiba Machinery Co., Ltd.) equipped with a pingate flat plate mold having a thickness of 150 mm × 150 mm × 2 mm. The pressure (gauge pressure 70 MPa), the injection speed (panel set value) 85%, and the injection time / cooling time = 10 sec / 30 sec were set, and the molded flat plate was continuously formed.
In continuous molding of 100 shots or less, the case where MD adhesion is visually observed on the mold is ×, the case where MD adhesion is visually observed on the mold after 200 shots is Δ, and the case where it is not observed is 〇, 300 shots. Later, those in which no MD adhesion was visually observed on the mold were evaluated as ⊚.
As the evaluation criteria, it was judged that the resin composition of the present embodiment was particularly preferable in the case of ⊚ in the case of ⊚ or more.

(7. Thin-walled flame-retardant)
Measurements were performed based on the UL-94 vertical combustion test method using five 0.7 mm-thick Tanzaku molded pieces, and the flame retardancy level was determined. In addition, the number of burning seconds at the time of the first flame contact and the second flame contact of each of the Tanzaku molded pieces was measured (5 pieces x 2 times for a total of 10 flame contact), and the minimum burning seconds and the maximum burning seconds were obtained. The difference was calculated.
In particular, when the flame retardancy level is V-0 determination and the difference between the minimum combustion seconds and the maximum combustion seconds is within 5 seconds, it is determined that the resin composition of the present embodiment is preferable.

〔raw materials〕
<Polyphenylene ether (A)>
(A-1)
Reduced viscosity 0.50 dL / g (0.5 g / dL chloroform solution, 30 ° C., measured with Ubbelohde viscometer), number average molecular weight 18300, terminal OH groups per 100 units: 0.71, N, per 100 units, N-dibutylaminomethyl group: 0.39 poly (2,6-dimethyl-1,4-phenylene) ether powder (A-1) was prepared by solution polymerization (hereinafter, simply "(A-1)). ").

(A-2)
The above 97 parts by mass of (A-1) and 3 parts by mass of maleic anhydride (manufactured by Mitsubishi Chemical Corporation) are mixed by a tumbler mixer, and this powder mixture is mixed with a twin-screw extruder (manufactured by Coperion, ZSK25 extruder). ) Is supplied from the first raw material supply port (top feed), melt-kneaded under the conditions of a barrel temperature of 300 ° C., a screw rotation speed of 300 rpm, an extrusion rate of 10 kg / hr, and a vent vacuum degree of 7.998 kPa (60 Torr), and pelleted. (A-2) was obtained (hereinafter, may be referred to as "(A-2)").
The pellet was dissolved in chloroform and then reprecipitated with methanol to extract the polyphenylene ether component. Then, it was vacuum dried at 60 degreeC for 4 hours, and the powder of polyphenylene ether (A-2) was obtained.
The obtained polyphenylene ether (A-2) powder can be identified by ¹ H-NMR, and the integral value of the peak appearing at 2.5 to 4.0 ppm of ¹ H-NMR is derived from the aromatic ring of polyphenylene ether. By dividing by the integral value of the peak of 6.0 to 7.0 ppm, it was confirmed that each 100 units of the polyphenylene ether monomer had 0.3 structures of the following chemical formula (4).

^{1 1} H-NMR measurement condition device: JEOL-ECA500
Observation nucleus: ¹ H
Observation frequency: 500.16MHz
Measurement method: Single-Pulse
Pulse width: 7 μsec
Waiting time: 5 seconds Accumulation number: 512 times Solvent: CDCl ₃
Sample concentration: 5w%
Chemical shift criteria: TMS 0.00ppm

<Polystyrene (B)>
(B-1) General Purpose Polystyrene (GPPS) (trade name: Polystyrene 680 [registered trademark], manufactured by Asahi Kasei Corporation) (hereinafter, may be referred to as “(B-1)”) was used.

<Condensation type phosphoric acid ester flame retardant (C)>
(C-1) Bisphenol A Bisdiphenyl phosphate (FR) (aromatic phosphate ester flame retardant, trade name: CR741 [registered trademark], manufactured by Daihachi Kagaku Co., Ltd.) (hereinafter referred to as "(C-1)" There is also).
(C-2) Compound (FR) represented by the following chemical formula (5) (solid property at room temperature (23 ° C.). Product name: PX-200 [registered trademark], manufactured by Daihachi Chemical Co., Ltd.) (hereinafter, " (C-2) ”) was used.

<Glass fiber (D)>
(D-1) Glass fiber (GF) having an average fiber diameter of 10 μm surface-treated with an aminosilane compound (trade name: EC10 3MM 910 [registered trademark], manufactured by NSG Vetrotex) (hereinafter, “(D-1)). ") Was used.

[Comparative Example 1]
(A-1) 57 parts by mass of ZSK40MC twin-screw extruder (kneading disc L: 2, kneading disc R: 6, kneading disc N) manufactured by Werner & Pfleiderer, Germany, having 13 barrels and a screw diameter of 40 mm. : Supply from the most upstream part (top feed) of the screw pattern having 4 pieces), add 13 parts by mass (C-1) from the barrel 5 in the middle using the liquid addition nozzle, and further from the barrel 8 in the middle. (D-1) 30 parts by mass was side-fed and melt-kneaded at a cylinder temperature of 300 ° C., a screw rotation speed of 300 rpm, and an extrusion rate of 100 kg / h to obtain a resin composition. Table 1 shows the results of the physical characteristic test of the resin composition.

[ Reference Example 1]
57 parts by mass of (A-1) and 0.5 parts by mass of (C-2) are supplied from the most upstream part (top feed) by using the twin-screw extruder used in Comparative Example 1 above. 12.5 parts by mass of (C-1) from the barrel 5 in the middle is added using a liquid addition nozzle, and 30 parts by mass of (D-1) is further side-fed from the barrel 8 in the middle, and the cylinder temperature is 300. A resin composition was obtained by melt-kneading at ° C., a screw rotation speed of 300 rpm, and an extrusion rate of 100 kg / h. Table 1 shows the results of the physical characteristic test of the resin composition.

[Example 2]
57 parts by mass of (A-1) and 1 part by mass of (C-2) are supplied from the most upstream part (top feed) by using the twin-screw extruder used in Comparative Example 1 above, and in the middle of the process. 12 parts by mass of (C-1) from the barrel 5 is added using a liquid addition nozzle, and 30 parts by mass of (D-1) is further side-fed from the barrel 8 in the middle, the cylinder temperature is 300 ° C., and the screw is rotated. A resin composition was obtained by melt-kneading at several 300 rpm and an extrusion rate of 100 kg / h. Table 1 shows the results of the physical characteristic test of the resin composition.

[Example 3]
(A-1) 52 parts by mass, (A-2) 5 parts by mass, and (C-2) 1 part by mass, using the twin-screw extruder used in Comparative Example 1 above, the most upstream part. It is supplied from (top feed), 12 parts by mass of (C-1) from barrel 5 in the middle is added using a liquid addition nozzle, and 30 parts by mass of (D-1) is further side-fed from barrel 8 in the middle. Then, the resin composition was obtained by melt-kneading at a cylinder temperature of 300 ° C., a screw rotation speed of 300 rpm, and an extrusion rate of 100 kg / h. Table 1 shows the results of the physical characteristic test of the resin composition.

[Example 4]
57 parts by mass of (A-1) and 3 parts by mass of (C-2) are supplied from the most upstream part (top feed) by using the twin-screw extruder used in Comparative Example 1 above. 10 parts by mass of (C-1) from the barrel 5 is added using a liquid addition nozzle, and 30 parts by mass of (D-1) is further side-fed from the barrel 8 in the middle, the cylinder temperature is 300 ° C., and the screw is rotated. A resin composition was obtained by melt-kneading at several 300 rpm and an extrusion rate of 100 kg / h. Table 1 shows the results of the physical characteristic test of the resin composition.

[Example 5]
57 parts by mass of (A-1) and 6 parts by mass of (C-2) are supplied from the most upstream part (top feed) by using the twin-screw extruder used in Comparative Example 1 above, and in the middle of the process. 7 parts by mass of (C-1) from the barrel 5 is added using a liquid addition nozzle, and 30 parts by mass of (D-1) is further side-fed from the barrel 8 in the middle, and the cylinder temperature is 300 ° C. and the screw is rotated. A resin composition was obtained by melt-kneading at several 300 rpm and an extrusion rate of 100 kg / h. Table 1 shows the results of the physical characteristic test of the resin composition.

[ Reference Example 6]
57 parts by mass of (A-1) and 8 parts by mass of (C-2) are supplied from the most upstream part (top feed) by using the twin-screw extruder used in Comparative Example 1 above. 5 parts by mass of (C-1) from the barrel 5 is added using a liquid addition nozzle, and 30 parts by mass of (D-1) from the barrel 8 on the way is side-fed, the cylinder temperature is 300 ° C., and the screw is rotated. A resin composition was obtained by melt-kneading at several 300 rpm and an extrusion rate of 100 kg / h. Table 1 shows the results of the physical characteristic test of the resin composition.

[ Reference Example 7]
(A-1) 57 parts by mass, (C-1) 2 parts by mass, and (C-2) 11 parts by mass, using the twin-screw extruder used in Comparative Example 1 above, the most upstream part. The resin composition is supplied from (top feed), side-fed 30 parts by mass (D-1) from the barrel 8 on the way, and melt-kneaded at a cylinder temperature of 300 ° C., a screw rotation speed of 300 rpm, and an extrusion rate of 100 kg / h. Got Table 1 shows the results of the physical characteristic test of the resin composition.

[ Reference Example 8]
57 parts by mass of (A-1) and 13 parts by mass of (C-2) are supplied from the most upstream part (top feed) by using the twin-screw extruder used in Comparative Example 1 above. 30 parts by mass of (D-1) was side-fed from the barrel 8 and melt-kneaded at a cylinder temperature of 300 ° C., a screw rotation speed of 300 rpm, and an extrusion rate of 100 kg / h to obtain a resin composition. Table 1 shows the results of the physical characteristic test of the resin composition.

[Comparative Example 2]
(A-1) 61 parts by mass and 9 parts by mass of triphenylphosphine (trade name: TPP [registered trademark], manufactured by Daihachi Chemical Co., Ltd.), which is a phosphoric acid ester flame retardant, were used in Comparative Example 1 above. Using a twin-screw extruder, supply from the most upstream part (top feed), side feed 30 parts by mass (D-1) from the barrel 8 on the way, cylinder temperature 300 ° C, screw rotation speed 300 rpm, extrusion rate. A resin composition was obtained by melt-kneading at 100 kg / h. Table 1 shows the results of the physical characteristic test of the resin composition.

[Example 9]
(A-1) 54 parts by mass, (B-1) 3 parts by mass, and (C-2) 3 parts by mass using the twin-screw extruder used in Comparative Example 1 above, the most upstream part. Supply from (top feed), add 10 parts by mass (C-1) from barrel 5 in the middle using a liquid addition nozzle, and further add 30 parts by mass (D-1) from barrel 8 in the middle to side feed. Then, the resin composition was obtained by melt-kneading at a cylinder temperature of 300 ° C., a screw rotation speed of 300 rpm, and an extrusion rate of 100 kg / h. Table 1 shows the results of the physical characteristic test of the resin composition.

[Example 10]
(A-1) 52 parts by mass, (B-1) 5 parts by mass, and (C-2) 3 parts by mass, using the twin-screw extruder used in Comparative Example 1 above, the most upstream part. Supply from (top feed), add 10 parts by mass (C-1) from barrel 5 in the middle using a liquid addition nozzle, and further add 30 parts by mass (D-1) from barrel 8 in the middle to side feed. Then, the resin composition was obtained by melt-kneading at a cylinder temperature of 300 ° C., a screw rotation speed of 300 rpm, and an extrusion rate of 100 kg / h. Table 1 shows the results of the physical characteristic test of the resin composition.

[Comparative Example 3]
(A-1) 51 parts by mass, (B-1) 6 parts by mass, and (C-2) 3 parts by mass, using the twin-screw extruder used in Comparative Example 1 above, the most upstream part. Supply from (top feed), add 10 parts by mass (C-1) from barrel 5 in the middle using a liquid addition nozzle, and further add 30 parts by mass (D-1) from barrel 8 in the middle to side feed. Then, the resin composition was obtained by melt-kneading at a cylinder temperature of 300 ° C., a screw rotation speed of 300 rpm, and an extrusion rate of 100 kg / h. Table 1 shows the results of the physical characteristic test of the resin composition.

[Example 11]
(A-1) 45 parts by mass and (C-2) 4 parts by mass are supplied from the most upstream part (top feed) by using the twin-screw extruder used in Comparative Example 1 above, and in the middle of the process. 11 parts by mass of (C-1) from barrel 5 is added using a liquid addition nozzle, and 40 parts by mass of (D-1) is side-fed from barrel 8 on the way, and the cylinder temperature is 300 ° C. and screw rotation. A resin composition was obtained by melt-kneading at several 300 rpm and an extrusion rate of 100 kg / h. Table 1 shows the results of the physical characteristic test of the resin composition.

[Comparative Example 4]
(A-1) 45 parts by mass and 15 parts by mass of a phosphazene-based flame retardant phosphonitrile acid phenyl ester (trade name: Ravitor FP-110 [registered trademark], manufactured by Fushimi Pharmaceutical Co., Ltd.) were used in Comparative Example 1 above. Using the twin-screw extruder used in, supply from the most upstream part (top feed), side-feed 40 parts by mass (D-1) from the barrel 8 on the way, cylinder temperature 300 ° C, screw rotation speed 300 rpm. , The resin composition was obtained by melt-kneading at an extrusion rate of 100 kg / h. Table 1 shows the results of the physical characteristic test of the resin composition.

[Example 12]
68 parts by mass of (A-1) and 4 parts by mass of (C-2) are supplied from the most upstream part (top feed) by using the twin-screw extruder used in Comparative Example 1 above. 13 parts by mass of (C-1) from the barrel 5 is added using a liquid addition nozzle, and 15 parts by mass of (D-1) is further side-fed from the barrel 8 in the middle, the cylinder temperature is 300 ° C., and the screw is rotated. A resin composition was obtained by melt-kneading at several 300 rpm and an extrusion rate of 100 kg / h. Table 1 shows the results of the physical characteristic test of the resin composition.

[Example 13]
(A-1) 80 parts by mass, (A-2) 3 parts by mass, and (C-2) 1 part by mass, using the twin-screw extruder used in Comparative Example 1 above, the most upstream part. It is supplied from (top feed), 5 parts by mass of (C-1) from barrel 5 in the middle is added using a liquid addition nozzle, and 11 parts by mass of (D-1) from barrel 8 in the middle is side-fed. Then, the resin composition was obtained by melt-kneading at a cylinder temperature of 300 ° C., a screw rotation speed of 300 rpm, and an extrusion rate of 100 kg / h. Table 1 shows the results of the physical characteristic test of the resin composition.

[Example 14]
(A-1) 23 parts by mass, (B-1) 2 parts by mass, and (C-2) 8 parts by mass, using the twin-screw extruder used in Comparative Example 1 above, the most upstream part. Supply from (top feed), 17 parts by mass of (C-1) from barrel 5 in the middle is added using a liquid addition nozzle, and 50 parts by mass of (D-1) from barrel 8 in the middle is side-fed. Then, the resin composition was obtained by melt-kneading at a cylinder temperature of 300 ° C., a screw rotation speed of 300 rpm, and an extrusion rate of 100 kg / h. Table 1 shows the results of the physical characteristic test of the resin composition.

[Example 15]
(A-1) 54 parts by mass, (C-2) 3 parts by mass, and 3 parts by mass of phenol terpene resin (trade name: YS Polystar T160 [registered trademark], manufactured by Yasuhara Chemical Co., Ltd.) are used in Comparative Example 1 above. Using the twin-screw extruder used in, supply from the most upstream part (top feed), add 10 parts by mass (C-1) from barrel 5 on the way using a liquid addition nozzle, and further on the way. 30 parts by mass of (D-1) was side-fed from the barrel 8 and melt-kneaded at a cylinder temperature of 300 ° C., a screw rotation speed of 300 rpm, and an extrusion rate of 100 kg / h to obtain a resin composition. Table 1 shows the results of the physical characteristic test of the resin composition.

From Table 1, since the resin composition of Comparative Example 1 contains only (C-1) and does not contain (C-2) as the component (C), there is a large variation in the number of burning seconds between the test pieces in the combustion test. Also, the flame retardancy is not sufficient.
In the resin compositions of Examples 2 to 5 and 11 to 15 , and Reference Examples 1 and 6 to 8 , the blending amounts of the components (A), (C), and (D) are all within the specified range of the present application. In the combustion test, the variation in the number of burning seconds between the test pieces was extremely small, and the balance of other physical properties was also good. In particular, in Examples 2 to 5 and 11 to 15, no MD (mold deposit) adhered to the mold even after the continuous molding of 300 shots was performed. On the other hand, in Reference Examples 1 and 6 to 8, MD adhesion was not observed in the mold up to 200 shots, but MD was slightly observed after 300 shots. That is, in Examples 2 to 5 and 11 to 15, the MD adhesion to the mold is further improved by containing (C1) in a proportion of 50 to 95% by mass and (C2) in a proportion of 50 to 5% by mass. There was a tendency to be. Although the cause is not clear, the presence of (C-1) and (C-2) in the composition in the above ratio causes the MD component to adhere to the surface layer portion of the molded body rather than the surface of the mold. It is presumed that this is because it becomes easier and it becomes difficult for MD to accumulate on the mold.
In Example 3, the DTUL, Charpy impact strength, tensile strength, and bending strength tended to be improved as compared with Example 2. This is a modified polyphenylene ether functionalized with maleic anhydride. By using the component (A-2) in combination with the component (A-1), the resin component and the glass fiber which is the component (D-1) adhere to each other. It is probable that the sex was improved.
In Comparative Example 2, a flame retardant component other than the component (C) of the present application was used, but a large amount of gas was generated during molding, which was not always sufficient in terms of the working environment. In addition, clear MD was observed in the mold from the vicinity of exceeding 20 shots of continuous molding. Although the physical properties and flame retardancy itself were at good levels, the result was that there was a large variation in the number of burning seconds between the test pieces in the combustion test.
In Examples 9 and 10, since the blending amounts of the components (A), (B), (C), and (D) are within the range of the present application, the variation in the number of burning seconds between the test pieces in the combustion test is small. , Other physical characteristics were well balanced. In Comparative Example 3, since the blending amount of the component (B) was out of the range specified in the present application, the flame retardancy was significantly reduced. In addition, the variation in the number of burning seconds between the test pieces in the combustion test was also large.
In Comparative Example 4, a flame retardant component other than the component (C) of the present application was used, but the molding fluidity was low and the molding processability was not always sufficient. In addition, MD generation was observed from around 50 shots during continuous molding. The variation in the number of burning seconds between the test pieces in the combustion test was also large.
Further, in particular, in Examples 2 to 4 and Reference Example 1 , when molded bodies having a thickness of 2.0 mm and a thickness of 0.5 mm were produced and a vertical combustion test was performed, the results were V-0.

The polyphenylene ether-based resin composition of the present invention has heat resistance and mechanical properties such as tensile strength and bending strength that can be effectively used even in a usage environment where long-term durability is required. Has extremely good flame retardancy in combustion tests with thin-walled molded pieces, and generates very little mold MD and gas during continuous molding. Therefore, resin molded bodies that are used for a long time under high temperature conditions, especially electricity. -It can be effectively used as a cooling fan for electronic devices.

Claims (9)

Contains polyphenylene ether (A), styrene resin (B), flame retardant (C), and glass fiber (D), and the total amount of the components (A), (B), (C), and (D). The content of each component with respect to 100% by mass is (A) component 20 to 84% by mass, (B) component 0 to 5% by mass, (C) component 5 to 25% by mass, and (D) component 11 to 50% by mass. The component (C) is 50 to 95 % by mass of bisphenol A bisdiphenyl phosphate (C-1) and condensed phosphorus represented by the following chemical formula (1) with respect to 100% by mass of the component (C). A polyphenylene ether-based resin composition, which is a mixture containing 50 to 5 % by mass of an acid ester-based flame retardant (C-2).

(In the formula, R ¹ to R ⁴ are 2,6-kisilyl groups, and n is 1 to 3). The polyphenylene ether-based resin according to claim 1, wherein the total content of the components (A), (B), (C), and (D) accounts for 90% by mass or more of the entire polyphenylene ether-based resin composition. Composition. The polyphenylene ether-based resin composition according to claim 1 or 2, wherein a part or all of the component (A) is a functionalized polyphenylene ether functionalized with a carboxylic acid or an acid anhydride. The polyphenylene ether-based resin composition according to any one of claims 1 to 3 , wherein the flame retardant level when a combustion test is carried out with a test piece having a thickness of 0.7 mm in accordance with UL94 is V-0. .. The polyphenylene ether-based resin composition according to claim 4 , wherein the difference between the maximum combustion seconds and the minimum combustion seconds is within 5.0 seconds when the vertical combustion test is carried out. A molded product comprising the polyphenylene ether-based resin composition according to any one of claims 1 to 5 . The molded product according to claim 6 , which has a thickness of 0.5 to 2.0 mm and has a flame retardancy level of V-0 when a vertical combustion test is carried out in accordance with UL94. The molded product according to claim 6 or 7 , which is a cooling fan for electrical / electronic equipment. Contains polyphenylene ether (A), styrene resin (B), flame retardant (C), and glass fiber (D), and the total amount of the components (A), (B), (C), and (D). The content of each component with respect to 100% by mass is (A) component 20 to 84% by mass, (B) component 0 to 5% by mass, (C) component 5 to 25% by mass, and (D) component 11 to 50% by mass. In the polyphenylene ether-based resin composition, which is based on UL94, the variation in combustion time when a vertical combustion test is performed on a test piece having a thickness of 0.7 mm (difference between the minimum combustion seconds and the maximum combustion seconds). Is a way to improve
As the flame retardant (C), bisphenol A bisdiphenyl phosphate (C-1) 50 to 95 % by mass and a condensed phosphoric acid ester represented by the following chemical formula (1) with respect to 100% by mass of the component (C). A method comprising the use of a mixture containing 50-5 % by mass of the flame retardant (C-2).

(In the formula, R ¹ to R ⁴ are 2,6-kisilyl groups, and n is 1 to 3).