JP2005132954A - Polyphenylene oxide-based resin composition and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition which gives a molding superior in tensile strength, bending elastic modulus, and heat resistance. <P>SOLUTION: The polyphenylene oxide-based resin compositin is formed by blending a polyphenylene oxide (A) which has a structural unit expressed by formula (1) where R<SB>1</SB>and R<SB>2</SB>are each independently a hydrogen atom or a 1 to 20C hydrocarbon group which may have a sustituent; a copolymer (B) which has a functional group having a reactivity on the polyphenylene oxide; and aluminium hydroxide (C). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a polyphenylene oxide resin composition excellent in tensile strength, flexural modulus, and heat resistance, and a method for producing the same.

  Polyphenylene oxide, a type of engineering plastic, has heat resistance and electrical insulation, and has a low dielectric constant compared to other engineering plastics such as polyethersulfone, polyetheretherketone, polyetherimide, and polyamideimide. And it is relatively inexpensive.

  As a resin composition using polyphenylene oxide, for example, a resin composition made of polyphenylene oxide and a copolymer having a functional group reactive with polyphenylene oxide is known (Patent Document 1).

However, such a resin composition may have insufficient tensile properties, bending elastic modulus, and heat resistance of a molded body using the resin composition depending on the application, and improvements have been demanded from the market.
An object of the present invention is to provide a resin composition that is excellent in tensile properties, bending elastic modulus, and heat resistance of a molded body using the resin composition.

JP 2002-319316 A

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have formulated a resin composition comprising polyphenylene oxide, a copolymer having a functional group reactive with polyphenylene oxide, and aluminum hydroxide. The present invention has been completed by finding that a molded article using a product has excellent tensile properties, flexural modulus, and heat resistance.

（式中、Ｒ_１およびＲ_２は、それぞれ独立に水素原子又は置換基を有することもある全炭素数１〜２０の炭化水素を表す。）
で示される構造単位を有するポリフェニレンオキサイドと（Ｂ）該ポリフェニレンオキサイドと反応性を有する官能基を持った共重合体と（Ｃ）水酸化アルミニウムとを配合してなるポリフェニレンオキサイド系樹脂組成物を提供するものである。 That is, the present invention
(A) The following formula (1)

(In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or a hydrocarbon having 1 to 20 carbon atoms which may have a substituent.)
A polyphenylene oxide-based resin composition comprising: (B) a copolymer having a functional group reactive with the polyphenylene oxide and (C) aluminum hydroxide. To do.

  A molded body using the polyphenylene oxide resin composition of the present invention is excellent in tensile strength, flexural modulus, and heat resistance.

  The polyphenylene oxide which is the component (A) of the polyphenylene oxide resin composition of the present invention is a polymer having a structural unit of the formula (1), and has two or more types of structural units of the formula (1). Also good.

Here, R ₁ and R ₂ each independently represent hydrogen or a hydrocarbon group having 1 to 20 carbon atoms that may have a substituent.
Examples of the hydrocarbon group having 1 to 20 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a t-butyl group, a pentyl group, and a cyclopentyl group. Alkyl groups having 1 to 20 carbon atoms such as hexyl group, cyclohexyl group, octyl group and decyl group; aryl groups having 6 to 20 carbon atoms such as phenyl group, 4-methylphenyl group, 1-naphthyl group and 2-naphthyl group; And an aralkyl group having 7 to 20 carbon atoms in total, such as a benzyl group, a 2-phenylethyl group, and a 1-phenylethyl group. When the hydrocarbon group has a substituent, examples of the substituent include a halogen atom such as a fluorine atom, an alkoxy group such as a t-butyloxy group, and a diarylamino group such as a 3-diphenylamino group. Specific examples of the hydrocarbon group having a substituent include a trifluoromethyl group, a 2-t-butyloxyethyl group, a 3-diphenylaminopropyl group, and the like. The total carbon number does not include the carbon number of the substituent.

Among these, R ₁ and R ₂ are preferably hydrogen, a methyl group or the like, and particularly preferably hydrogen.

  Even if the polyphenylene oxide of component (A) is a homopolymer having the structural unit of the above formula (1), it is a single amount that is a phenol compound other than the phenol compound corresponding to (1) in addition to the above formula (1) A copolymer having a structural unit derived from a body may be used. Examples of such a phenol compound include polyvalent hydroxyaromatic compounds (for example, bisphenol-A, tetrabromobisphenol-A, resorcin, hydroquinone, and novolak resin). Such a copolymer preferably contains 80 mol% or more, more preferably 90 mol% or more of the structural unit represented by formula (1).

In addition, the intrinsic viscosity [η] of the component (A) in the present invention is preferably in the range of 0.30 to 0.65, more preferably 0.35 to 0.50 (25 ° C., chloroform solution).
When [η] is less than 0.30, the heat resistance of the composition tends to decrease, and when [η] exceeds 0.65, the moldability of the composition tends to decrease.

（式中、Ｒ_１およびＲ_２は前記と同じ意味を表す。）
で示されるフェノール化合物を酸化重合させて製造することができる。 The polyphenylene oxide of component (A) is, for example, the following formula (2)

(Wherein R ₁ and R ₂ represent the same meaning as described above.)
It can be produced by oxidative polymerization of a phenol compound represented by

When only the phenol compound of the above formula (2) is used as a raw material, the above homopolymer can be produced. Further, in addition to the above formula (2), by using a phenol compound other than (2), A polymer can be produced.

  The oxidative polymerization can be performed using the above phenol compound using an oxidative coupling catalyst and using, for example, oxygen or an oxygen-containing gas as an oxidant. The oxidative coupling catalyst is not particularly limited, and any catalyst having a polymerization ability can be used. For example, typical examples thereof include a catalyst containing cuprous chloride and a catalyst containing divalent manganese salts (Japanese Patent Laid-Open No. 60-229923).

  The resin composition of the present invention comprises a copolymer having a functional group having reactivity with the polyphenylene oxide of the component (B) in addition to the polyphenylene oxide of the component (A) as described above. The functional group having reactivity with the polyphenylene oxide may be reactive with the component (A), and examples thereof include an oxazolyl group, an epoxy group, and an amino group. An epoxy group is preferable.

  Examples of the copolymer include those having a structural unit having the functional group and a structural unit not having the functional group.

  As the structural unit having a functional group, a structural unit containing a glycidyl group is preferred as the functional group being an epoxy group. Examples of the structural unit include an unsaturated carboxylic acid glycidyl ester unit and / or an unsaturated glycidyl ether unit. Here, the unsaturated carboxylic acid glycidyl ester unit and the unsaturated glycidyl ether unit refer to a structural unit derived from a monomer that is an unsaturated carboxylic acid glycidyl ester or an unsaturated glycidyl ether.

（式中、Ｒは、エチレン系不飽和結合を有する炭素数２〜１３の炭化水素基を表し、Ｘは、−Ｃ(Ｏ)Ｏ−、−ＣＨ₂−Ｏ−または

を表す。）
で示されるものが挙げられる。 Here, as unsaturated carboxylic acid glycidyl ester and unsaturated glycidyl ether, for example, the following general formula

(In the formula, R represents a hydrocarbon group having 2 to 13 carbon atoms having an ethylenically unsaturated bond, and X represents —C (O) O—, —CH ₂ —O— or

Represents. )
The thing shown by is mentioned.

Specific examples of the unsaturated carboxylic acid glycidyl ester include glycidyl acrylate, glycidyl methacrylate, itaconic acid diglycidyl ester, butenetricarboxylic acid triglycidyl ester, p-styrene carboxylic acid glycidyl ester, and the like. Unsaturated glycidyl ether Specific examples of these include vinyl glycidyl ether, allyl glycidyl ether, 2-methylallyl glycidyl ether, and styrene-p-glycidyl ether.

  Examples of the structural unit having no functional group in the copolymer of component (B) include a structural unit derived from a monomer that is a compound having an ethylenically unsaturated bond, and the compound includes (meth) acrylic acid. Examples thereof include acrylic esters such as alkyl esters and alkoxyalkyl esters of acrylic acid, ethylene, vinyl aromatic hydrocarbon compounds, ethylene unsaturated ester compounds, conjugated diene compounds, and ethylene unsaturated ester compounds.

  The copolymer of the component (B) has 0.1 to 30 mass of such unsaturated carboxylic acid glycidyl ester unit and / or unsaturated glycidyl ether unit when the total structural unit of the copolymer is 100 mass%. % Content is preferable, and 0.1 to 20% by mass is more preferable.

  Among the copolymers which are component (B), those containing unsaturated carboxylic acid glycidyl ester units and / or unsaturated glycidyl ether units include, for example, unsaturated glycidyl carboxylates represented by the above general formula (2). It can be produced by copolymerizing an ester and / or an unsaturated glycidyl ether with a compound having an ethylenically unsaturated bond.

  Moreover, the copolymer which is a component (B) can also be manufactured by graft-copolymerizing the monomer which has this functional group to a copolymer.

  The copolymer (B) may be a rubber or a thermoplastic resin, or may be a mixture of rubber and a thermoplastic resin.

First, the rubber as the component (B) of the present invention will be described.
Examples of the rubber as the component (B) of the present invention include acrylic rubber having a functional group reactive with polyphenylene oxide, and vinyl aromatic hydrocarbon compound-conjugated diene compound block having a functional group reactive with polyphenylene oxide. Copolymer rubber can also be illustrated.

The acrylic rubber having a functional group reactive with polyphenylene oxide is preferably represented by the general formulas (8) to (10).
^{_{CH 2 = CR 7 -C (O}} ) -OR 1 (8)
^{_{CH 2 = CR 8 -C (O}} ) -OR 2 OR 3 (9)
^{_{CH 2 = CR 4 H-C}} (O) -O (R 5 (C (O) O) nR 6 (10)
(In the formula, R ¹ represents an alkyl group having 1 to 18 carbon atoms (preferably 1 to 8) or a cyanoalkyl group having 1 to 18 carbon atoms. R ² represents an alkylene group having 1 to 12 carbon atoms. , R ³ represents an alkyl group having 1 to 12 carbon atoms, R ⁴ , R ⁷ and R ⁸ each independently represents a hydrogen atom or a methyl group, R ⁵ represents an alkylene group having 3 to 30 carbon atoms, R ⁶ Represents an alkyl group having 1 to 20 carbon atoms or a derivative thereof, and n represents an integer of 1 to 20).
And at least one monomer selected from the compounds represented by formula (1) and a monomer having a functional group reactive with polyphenylene oxide.

Specific examples of the (meth) acrylic acid alkyl ester represented by the general formula (8) include, for example, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, tert-butyl acrylate, butyl acrylate, pentyl acrylate, and hexyl. Acrylate, actyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, cyanoethyl acrylate, methyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, and the like. Methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, tert-butyl acrylate, t rt- butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate are preferred.
In addition, as (meth) acrylic acid ester, the 1 type may be used independently or 2 or more types may be used together.

  Examples of the acrylic acid alkoxyalkyl ester represented by the general formula (9) include, for example, methoxyethyl acrylate, ethoxyethyl acrylate, butoxyethyl acrylate, ethoxypropyl acrylate, methoxyethyl methacrylate, ethoxyethyl methacrylate, butoxyethyl methacrylate. Examples thereof include acrylate and ethoxypropyl methacrylate. One or more of these can be used as a component of the acrylic rubber.

As a constituent component of the acrylic rubber, an unsaturated monomer copolymerizable with at least one monomer selected from the compounds represented by the general formulas (8) to (10) is used as necessary. Can do.
Examples of such unsaturated monomers include ethylene, styrene, α-methyl styrene, acrylonitrile, halogenated styrene, methacrylonitrile, acrylamide, methacrylamide, vinyl naphthalene, N-methylol acrylamide, vinyl acetate, vinyl chloride. , Vinylidene chloride, benzyl acrylate, methacrylic acid, itaconic acid, fumaric acid, maleic acid and the like.

  As the monomer having a functional group reactive with polyphenylene oxide, unsaturated carboxylic acid glycidyl ester and / or unsaturated glycidyl ether are preferable. In this case, the preferable component ratio is at least one monomer selected from the compounds represented by the general formulas (8) to (10) 40.0 to 99.9% by mass, unsaturated carboxylic acid glycidyl ester, and And / or at least one monomer selected from the compounds represented by the above general formulas (8) to (10), 0.1 to 30% by weight, preferably 0.1 to 20% by weight, of unsaturated glycidyl ether; The copolymerizable unsaturated monomer is 0.0 to 30% by mass. When the component ratio of the acrylic rubber is within the above range, the composition has good heat resistance, moldability and the like, which is preferable.

  The method for producing the acrylic rubber is not particularly limited, and is described, for example, in JP-A-59-1113010, JP-A-62-64809, JP-A-3-160008, or WO95 / 04764. Such a known polymerization method can be used, and it can be produced by emulsion polymerization, suspension polymerization, solution polymerization or bulk polymerization in the presence of a radical initiator.

  Among the copolymers (B), rubber having an epoxy group is preferable, and (meth) acrylic acid ester-ethylene- (unsaturated carboxylic acid glycidyl ester and / or an (acrylic) rubber having an epoxy group. Unsaturated glycidyl ether) copolymer rubber and the like are more preferable.

The copolymer (B) having a Mooney viscosity of 3 to 70 is preferable, 3 to 30 is more preferable, and 4 to 25 is particularly preferable.
The Mooney viscosity here refers to a value measured using a 100 ° C. large rotor according to JIS K6300.

In order to improve the thermal stability and mechanical properties of the molded product obtained using the resin composition of the present invention, the (meth) acrylic acid ester unit is 40% by mass with respect to the entire structural unit of the copolymer. More than 96% by mass, more preferably 45 to 70% by mass, ethylene units 3% by mass or more and less than 50% by mass, more preferably 10 to 49% by mass, unsaturated carboxylic acid glycidyl ether unit and / or unsaturated glycidyl. The ether unit is 0.1 to 30% by mass, more preferably 0.1 to 20% by mass. (Representative polymerization methods: methods described in JP-A-48-11388, JP-A-61-127709, etc., for example, in the presence of a polymerization initiator that generates free radicals, a pressure of 500 kg / cm ² or more And can be produced under conditions of a temperature of 40 to 300 ° C.)

Examples of the vinyl aromatic hydrocarbon compound in the vinyl aromatic hydrocarbon compound-conjugated diene compound block copolymer rubber having a functional group reactive with polyphenylene oxide include styrene, vinyl toluene, divinylbenzene, and α-methylstyrene. , P-methylstyrene, vinylnaphthalene, etc., among which styrene is preferable. Examples of the conjugated diene compound include butadiene, isoprene, 1,3-pentadiene, 3-butyl-1,3-octadiene, and butadiene or isoprene is preferable.
Such a vinyl aromatic hydrocarbon compound-conjugated diene compound block copolymer or a hydrogenated product thereof can be produced by a known method, for example, Japanese Patent Publication No. 40-23798 and Japanese Patent Publication No. 59-133203. Etc. are described.
The vinyl aromatic hydrocarbon compound-conjugated diene compound block copolymer rubber having a functional group reactive with polyphenylene oxide in the present invention is a vinyl aromatic hydrocarbon compound-conjugated diene compound block obtained by the above-described method or the like. It can be obtained by introducing a monomer having reactivity with polyphenylene oxide, such as an epoxy group, into the copolymer. The method for introducing such a monomer into the vinyl aromatic hydrocarbon compound-conjugated diene compound block copolymer is not particularly limited, but it is preferably introduced by graft copolymerization or the like.

  The rubber as the copolymer (B) used in the present invention can be vulcanized as necessary and used as a vulcanized rubber.

  Vulcanization of the (meth) acrylic acid ester-ethylene- (unsaturated carboxylic acid glycidyl ester and / or unsaturated glycidyl ether) copolymer rubber is a polyfunctional organic acid, a polyfunctional amine compound, an imidazole compound, etc. However, the present invention is not limited to these.

The copolymer (B) having a functional group reactive with polyphenylene oxide can also be a resin in addition to the rubber as described above, and as a specific example of a thermoplastic resin having an epoxy group. (A) 60-99 mass% of ethylene units, (b) 0.1-20 mass% of unsaturated carboxylic acid glycidyl ester units and / or unsaturated glycidyl ether units, (c) ethylenically unsaturated ester compounds An epoxy group-containing ethylene copolymer having units of 0 to 40% by mass can be exemplified.

(B) Definitions and specific examples of unsaturated carboxylic acid glycidyl ester units and / or unsaturated glycidyl ether units are the same as described above.

  Examples of the ethylenically unsaturated ester compound (c) include vinyl acetate, vinyl propionate, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and other carboxylic acid vinyl esters, Examples include α, β-unsaturated carboxylic acid alkyl esters. In particular, vinyl acetate, methyl acrylate, and ethyl acrylate are preferable.

  Examples of the epoxy group-containing ethylene copolymer include a copolymer comprising an ethylene unit and a glycidyl methacrylate unit, a copolymer comprising an ethylene unit, a glycidyl methacrylate unit and a methyl acrylate unit, an ethylene unit, a glycidyl methacrylate unit and acrylic acid. Examples thereof include a copolymer composed of ethyl units, a copolymer composed of ethylene units, glycidyl methacrylate units and vinyl acetate units.

  The melt index (hereinafter sometimes referred to as MFR. JIS K6760, 190 ° C., 2.16 kg load) of the epoxy group-containing ethylene copolymer is preferably 0.5 to 100 g / 10 minutes, more preferably 2 to 50 g. / 10 minutes. The melt index may be outside this range, but if the melt index exceeds 100 g / 10 min, it is not preferable in terms of mechanical properties when it is made into a composition, and if it is less than 0.5 g / 10 min, component (A) The compatibility with is inferior.

The epoxy group-containing ethylene copolymer is preferably in the range stiffness modulus of 10~1300kg / cm ^2, further preferably from 20~1100kg / cm ^2. If the flexural modulus is outside this range, the mechanical properties of the composition may be insufficient.

  The copolymer (B) is preferably a copolymer having a heat of fusion of crystals of less than 3 J / g in order to improve the thermal stability and flexibility of the molded article of the present invention.

  The epoxy group-containing ethylene copolymer is usually an unsaturated epoxy compound and ethylene in the presence of a radical generator at 500 to 4000 atm and 100 to 300 ° C. in the presence or absence of a suitable solvent or chain transfer agent. It is produced by a high pressure radical polymerization method for copolymerization. It can also be produced by a method in which an unsaturated epoxy compound and a radical generator are mixed with polyethylene and melt graft copolymerized in an extruder.

Component (C) in the present invention is aluminum hydroxide, preferably having a bulk specific gravity of 0.1 g / cm ³ or more and 0.6 g / cm ³ or less, and a BET specific surface area of 30 m ² / g or more. Aluminum hydroxide that is less than 350 m ² / g is more preferred. When aluminum hydroxide having a bulk specific gravity or a BET specific surface area within the above range is used, the effect of improving tensile properties, flexural modulus, heat resistance, etc. is greatly preferred.
Further preferred aluminum hydroxide has a boehmite type crystal structure in addition to the above characteristics.
A well-known method can be used to produce aluminum hydroxide used in the present invention. Moreover, what has the characteristic of said numerical range can be obtained by the method as described in Unexamined-Japanese-Patent No. 2001-180929, for example. In addition, by adding aluminum hydroxide, in addition to the effect of excellent tensile properties, flexural modulus, and heat resistance. The effect of improving flame retardancy can also be achieved.

In the composition of the resin composition of the present invention, the ratio of the component (A) to the component (B)
Component (A) is usually 99 to 1% by weight, preferably 99 to 40% by weight, and component (B) is usually 1 to 99% by weight, preferably 1 to 60% by weight. When the component (A) exceeds 99% by weight, the moldability of the films tends to decrease. When the component (A) is less than 40% by weight, the heat resistance of the resin composition tends to be remarkably lowered.
The compounding ratio of the component (C) is usually 0.01 to 60 parts by weight, preferably 0.1 to 40 parts by weight with respect to 100 parts by weight of the sum of the components (A) and (B). If the blending ratio of component (C) is less than 0.01 parts by weight, the effect of improving the tensile strength, flexural modulus, and heat resistance tends to be reduced, and the blending ratio of component (C) is 60 parts by weight. If it exceeds, the molding of the resin composition tends to be difficult.

  The resin composition of the present invention may contain, as necessary, an organic filler, an antioxidant, a heat stabilizer, a light stabilizer, a lubricant, an inorganic or organic colorant, a rust inhibitor, a crosslinking agent, a foaming agent, and a fluorescent agent. In addition, various additives such as a surface smoothing agent, a surface gloss improving agent, and a mold release improving agent such as a fluororesin may be contained.

As a method for producing the resin composition of the present invention, a known method can be used, but a method of kneading (melt-kneading) each component in a molten state is preferable. In order to obtain the composition of the present invention by melt kneading, generally used kneading apparatuses such as a uniaxial or biaxial extruder and various kneaders can be used. Of these, a twin-screw extruder is preferable.
In melt kneading, the cylinder set temperature of the kneading apparatus is preferably in the range of 200 to 340 ° C, more preferably in the range of 220 to 310 ° C.

  At the time of melt kneading, each component may be supplied to the kneading apparatus after the components are uniformly mixed in advance by a device such as a tumbler or a Henschel mixer, or a method in which each component is separately metered into the kneading apparatus. Can also be used.

Obtaining a molded body by molding the above resin composition into a desired shape by various molding methods such as extrusion molding, injection molding, rotational molding, blow molding, blow molding, transfer molding, press molding, and solution casting. Can do. These molded bodies are called an extrusion molded body, an injection molded body, a rotational molded body, a blow molded body, a blow molded body, a transfer molded body, a press molded body, and a solution cast method molded body in order according to the molding method.
The shapes of these molded products include films (films, sheets, etc.), plates, filaments, non-woven fabrics, woven fabrics, tubes, tubes, containers, deformed products, home appliance parts, power transmission parts, automobile parts (bumpers, Instruments, etc.).

  In order to obtain films by molding the resin composition of the present invention, for example, a method of supplying the resin composition to an extruder equipped with a die (die) can be used.

As a die used for manufacturing films, a T die and a cylindrical slit die are preferably used.
A casting method, a hot press method, and the like can also be applied to the production of films based on Patent Document 1.

  When the said molded object is films, the thickness is not specifically limited, However, The range of 1-1000 micrometers is preferable practically, The range of 1-500 micrometers is more preferable. The surface of the film can be subjected to a surface treatment as necessary. Examples of such surface treatment methods include corona discharge treatment, plasma treatment, flame treatment, infrared treatment, sputtering treatment, solvent treatment, and polishing treatment. These treatments may be performed during the molding process or may be performed on the film or sheet after the molding process. However, such a process may be performed in the molding process, particularly before the winder. preferable.

  In addition, in order to obtain a hollow molded body such as a container or a bottle by molding the resin composition, a fluid pressure such as air or water is blown into the resin composition using, for example, a blow molding machine. A method (blow molding) for closely adhering to the mold can be used. Injection molding can also be applied.

  Moreover, in order to shape | mold said resin composition and obtain a pipe | tube and a tube, the method of melt-extruding the said resin composition to a tube die from an extruder can be used using a tube molding machine.

  Further, in order to obtain the filament by molding the above resin composition, a method in which the resin composition is melt-extruded to a strand die by an extruder and then wound at a high speed can be used.

  In addition, in order to obtain home appliance parts, electric parts, automobile parts (bumpers, instruments, etc.) by injection molding the above resin composition, the above resin composition melted using an injection molding machine Can be used at a high pressure from the extruder into the mold.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited only to these.

(1) Physical property measurement
(i) Deflection temperature under load (heat resistance)

The resin test piece was cut into strips, and the temperature at which the test piece reached a certain deflection (load deflection temperature) was measured with a load of 18.5 kg according to JIS K-7191.

(ii) Tensile strength, elongation rate Using an Autograph A-10TD model manufactured by Shimadzu Corporation, a tensile test was performed at room temperature and at a tensile speed of 5 mm / min in accordance with JIS K-7161, and the sample was broken. The tensile strength and elongation at that time were measured. Asked.

(iii) Bending elastic modulus A resin test piece was cut into a strip shape and subjected to a bending test at a bending speed of 1.5 mm / min in accordance with JIS K-7171 to obtain a bending elastic modulus.

(2) Resin composition component (A)
As a component (A), Mitsubishi Gas Chemical Co., Ltd. make, polyphenylene ether, YPX-100D ([(eta)] = 0.4) was used.
Ingredient (B)
As the component (B), Sumitomo Chemical Co., Ltd., Bond Fast E (ethylene / glycidyl methacrylate = 88/12 weight ratio, MFR (190 ° C.) = 3 g / 10 min) was used.
Ingredient (C)
The aluminum hydroxide used for component (C) is as follows.
C-1
Aluminum hydroxide manufactured by Sumitomo Chemical Co., Ltd.
BET specific surface area: 150 to 300 m ² / g, bulk specific gravity: 0.2 g / cm ³
Crystal: Boehmite type

Example 1
The component (A) and the component (C-1) (C-1) are dried at 120 ° C. for 8 hours, the component (B) is dried at 60 ° C. for 2 hours, and then the component (A) / component ( After mixing well at a ratio of B) / (C-1) = 76/24/5 (weight ratio), Technobel Co., Ltd. twin screw extruder, TZW-15-30MG (screw diameter 15 mm, L / D = 30) was used, and melt kneading was performed while degassing with a vent at a cylinder set temperature, a cylinder set temperature of 282 ° C., and a screw rotation speed of 200 rpm.
The pellets of the obtained composition were used in an injection molding machine NIIGATA NN75 manufactured by Niigata Iron Works Co., Ltd., a cylinder set temperature of 295 ° C., a mold temperature of 90 ° C., an injection pressure of 1630 Kg / cm ² , and an extruder screw rotation speed Injection molding was performed at 50 rpm. As the mold, a dumbbell-shaped mold having a length of 175 mm, a thickness of 3.2 mm, and a width of a constricted portion of 12.5 mm was used. By such injection molding, a test piece having a uniform light brown appearance and a smooth surface could be obtained. Hereinafter, this test piece may be abbreviated as AA-1. The physical property measurement results of AA-1 are as shown in Table 1.

Comparative Example 1
A melt-kneading and injection molding machine was performed in the same manner as in Example 1 except that (C-1) was not used, to obtain a dumbbell-shaped test piece having a light brown appearance and a smooth surface. Hereinafter, this test piece is abbreviated as BB-1. Table 1 shows the results of measuring the physical properties of the test piece.

Example 2
The component (A) and the component (C-1) (C-1) are dried at 120 ° C. for 8 hours, the component (B) is dried at 60 ° C. for 2 hours, and then the component (A) / component ( After mixing well at a ratio of B) / (C-1) = 92/8/2 (weight ratio), Technobel Co., Ltd. twin screw extruder, TZW-15-30MG (screw diameter 15 mm, L / D = 30) was used, and melt kneading was performed while degassing with a vent at a cylinder set temperature, a cylinder set temperature of 288 ° C., and a screw rotation speed of 200 rpm.
The pellet of the obtained composition was used in a polylab system manufactured by Hake Co., Ltd. (Germany) equipped with a T die, and the single screw extruder had a screw diameter of 19.05 mm and L / D = 20, and the cylinder set temperature. Kneading and extrusion were performed at 290 ° C. and a screw rotation speed of 33 rpm. A T die having a slit gap of 0.8 mm and a die width of 100 mm was used, and film formation was performed at a resin temperature of 290 ° C. in the T die. The resin temperature in the T die was detected by a temperature detector on the lower wall surface of the die part approximately 2 cm inside from the T die exit. The resin from the T-die was wound up at 4 m / min using a three-roll winder. The obtained film had a thickness of 230 μm, good appearance, and the maximum tensile strength was MD 830 Kg / cm ² , TD 520 Kg / cm ² elongation MD 23%, TD 9%.

Claims (17)

(A) The following formula (1)

(In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.)
A polyphenylene oxide resin composition comprising a polyphenylene oxide having a structural unit represented by formula (B), (B) a copolymer having a functional group reactive with the polyphenylene oxide, and (C) aluminum hydroxide. The composition according to claim 1, wherein the component (C) is aluminum hydroxide having a bulk specific gravity of 0.1 g / cm ³ or more and 0.6 g / cm ³ or less. Component (C) is aluminum hydroxide having a bulk specific gravity of 0.1 g / cm ³ or more and 0.6 g / cm ³ or less and a BET specific surface area of 30 m ² / g or more and less than 350 m ² / g. A composition according to claim 2 characterized.     The composition according to any one of claims 1 to 3, wherein the crystal structure of aluminum hydroxide as the component (C) is boehmite type.   The composition according to any one of claims 1 to 4, wherein the copolymer (B) having a functional group reactive with polyphenylene oxide is a copolymer having an epoxy group.   6. The copolymer according to claim 1, wherein the copolymer having an epoxy group is a copolymer containing 0.1 to 30% by mass of an unsaturated carboxylic acid glycidyl ester unit and / or an unsaturated glycidyl ether unit. Composition.   The composition according to any one of claims 1 to 6, wherein the heat of fusion of the copolymer (B) is less than 3 J / g.   The composition according to any one of claims 1 to 7, wherein the copolymer (B) has a Mooney viscosity in the range of 3 to 70.   The copolymer having an epoxy group comprises (a) 60 to 99% by mass of ethylene units, (b) 0.1 to 20% by mass of unsaturated carboxylic acid glycidyl ester units and / or unsaturated glycidyl ether units, (c The composition according to any one of claims 5 to 8, which is an epoxy group-containing ethylene copolymer comprising 0 to 40% by mass of an ethylenically unsaturated ester compound unit.   The composition according to any one of claims 5 to 8, wherein the copolymer having an epoxy group is a rubber having an epoxy group.   11. The composition according to claim 10, wherein the rubber having an epoxy group comprises a (meth) acrylic acid ester-ethylene- (unsaturated carboxylic acid glycidyl ester and / or unsaturated glycidyl ether) copolymer rubber. .   (Meth) acrylic acid ester is at least one selected from methyl acrylate, methyl methacrylate, n-butyl acrylate, n-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate 12. A composition according to claim 11 comprising. The method for producing a polyphenylene oxide resin composition according to any one of claims 1 to 12, wherein the (A), (B) and (C) are melt-kneaded.   The molded object which uses the polyphenylene oxide resin composition in any one of Claims 1-12.   An injection-molded article formed using the polyphenylene oxide-based resin composition according to claim 1.   A press-molded body comprising the polyphenylene oxide-based resin composition according to any one of claims 1 to 12. The shape of a molded object is a film, a tube, a pipe | tube, a bottle, or a container, The molded object in any one of Claims 14-16.