CN108117738A - Resin combination - Google Patents

Abstract

The present invention relates to resin compositions. An object of the present invention is to provide a resin composition excellent in impact resistance and vibration fatigue properties while maintaining whiteness. The resin composition of the present invention is characterized in that it contains 40 to 99 parts by mass of (a) polyphenylene ether resin and (b) inorganic filler in total of 100 parts by mass, (b) 1 mass part - 60 mass parts of inorganic fillers, (c) 0.1 mass parts - 5 mass parts of titanium oxide, (d) 0.3 mass parts - 10 mass parts of calcium carbonate.

Description

resin composition

technical field

The present invention relates to resin compositions. More specifically, it relates to a resin composition excellent in impact resistance and vibration fatigue properties used as home appliance parts, OA equipment parts, audio-visual equipment parts, automobile parts, and the like.

Background technique

Polyphenylene ether-based resins are used in various fields such as electronic/electrical parts, OA equipment parts, audio-visual equipment parts, and automobile parts as molding materials excellent in heat resistance, dimensional stability, and flame retardancy.

In recent years, in order to reduce the size, precision and weight of resin parts, there has been a strong demand for improvements in fluidity and impact resistance during hot-melt processing. However, the inorganic filler-added polyphenylene ether-based resin colored white obviously has a problem that impact resistance and vibration fatigue characteristics are significantly reduced.

For this reason, many improvement methods using elastomers have been proposed in terms of materials. However, in the resin composition to which the inorganic filler is added and colored white, the impact resistance imparting effect by adding an elastomer is small, and it is not practical.

Furthermore, from the viewpoint of appearance and prevention of assembling errors, it is impossible to stop the white coloring.

At present, a specific solution to this problem has not been disclosed, and an improved resin composition is expected.

Contents of the invention

The problem to be solved by the invention

The problem to be solved by the present invention is to provide a resin composition excellent in impact resistance and vibration fatigue characteristics while maintaining whiteness.

Solution to the problem

The present invention has conducted in-depth research to solve the above-mentioned problems. As a result, it has been found that a resin composition with a specific amount of polyphenylene ether resin, inorganic filler, titanium oxide, and calcium carbonate can obtain good durability while maintaining whiteness. Shock and vibration fatigue characteristics, thus completing the present invention.

That is, the present invention is as follows.

[1]

A resin composition, characterized in that,

Contains:

(a) 40 to 99 parts by mass of polyphenylene ether resin,

(b) 1 to 60 parts by mass of inorganic filler,

(c) 0.1 to 5 parts by mass of titanium oxide,

(d) 0.3 mass parts - 10 mass parts of calcium carbonate.

[2]

The resin composition as described in [1] whose average particle diameter of (d) calcium carbonate is 0.1 micrometer - 10 micrometers.

[3]

The resin composition as described in [1] or [2], wherein,

(a) polyphenylene ether-based resins include polyphenylene ether and polystyrene-based resins,

The mass ratio of the polyphenylene ether to the polystyrene resin (polyphenylene ether/polystyrene resin) is 99/1 to 5/95.

[4]

The resin composition according to [3], wherein the polystyrene-based resin is atactic polystyrene and/or high-impact polystyrene.

[5]

The resin composition according to any one of [1] to [4], which contains (e) condensed phosphoric acid with respect to a total of 100 parts by mass of (a) polyphenylene ether resin and (b) inorganic filler 2 to 20 parts by mass of the ester-based flame retardant.

[6]

The resin composition according to any one of [1] to [5], which contains (f) an elastomer based on 100 parts by mass of the total of (a) polyphenylene ether resin and (b) inorganic filler 1 to 20 parts by mass.

[7]

The resin composition according to [6], wherein the (f) elastomer is a block copolymer and/or a hydrogenated block copolymer.

The effect of the invention

According to the present invention, it is possible to provide a resin composition excellent in impact resistance and vibration fatigue properties while maintaining whiteness.

Detailed ways

A mode for carrying out the present invention (hereinafter referred to as "the present embodiment") will be described in detail below. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the gist.

[resin composition]

The resin composition of this embodiment contains (a) polyphenylene ether resin (sometimes described as "(a) component" in this specification), (b) inorganic filler (sometimes described as "(b) component" in this specification ), (c) titanium oxide (sometimes referred to as "(c) component" in this specification), and (d) calcium carbonate (sometimes described as "(d) component" in this specification), relative to (a) component and ( For 100 parts by mass of the total of components b), the content of component (a) is 40 parts by mass to 99 parts by mass, the content of component (b) is 1 part by mass to 60 parts by mass, and the content of component (c) is 0.1 parts by mass to 5 mass parts, (d) component is 0.3 mass parts - 10 mass parts.

With such a configuration, the resin composition of the present embodiment can exhibit excellent impact resistance and vibration fatigue characteristics while maintaining whiteness.

Next, the constituent components of the resin composition of the present embodiment will be described.

((a) Polyphenylene ether resin)

Since the resin composition of this embodiment contains (a) polyphenylene ether-type resin (it may abbreviate as "PPE-type resin" in this specification), it is excellent in flame retardancy and heat resistance.

The aforementioned PPE-based resin preferably includes polyphenylene ether (sometimes referred to as "PPE" in this specification) and polystyrene-based resin, and may be a mixed resin composed of PPE and polystyrene-based resin, or may be composed of only PPE. resin.

Since the above-mentioned PPE-based resin contains PPE, the flame retardancy and heat resistance of the resin composition of this embodiment are further excellent.

As said PPE, the homopolymer which consists of the repeating unit structure represented by following formula (1), and the copolymer which has the repeating unit structure represented by following formula (1) are mentioned, for example.

One of the above PPEs may be used alone, or two or more of them may be used in combination.

【Chemical 1】

In the above formula (1), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, a primary alkyl group with 1 to 7 carbon atoms, and a secondary alkane with 1 to 7 carbon atoms. A monovalent group in the group consisting of radical, phenyl, haloalkyl, aminoalkyl, hydrocarbyloxy, and halohydrocarbyloxy having at least 2 carbon atoms separating the halogen atom from the oxygen atom.

For the above-mentioned PPE, from the aspects of fluidity, toughness and chemical resistance during processing, the reduced viscosity measured with a Ubbelohde viscometer at 30°C using a chloroform solution with a concentration of 0.5g/dL is preferred. It is 0.15dL/g-2.0dL/g, More preferably, it is 0.20dL/g-1.0dL/g, More preferably, it is 0.30dL/g-0.70dL/g.

Examples of the aforementioned PPE include, but are not limited to, poly(2,6-dimethyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), poly(2-methyl-6-phenyl-1,4-phenylene ether), poly(2,6-dichloro-1,4-phenylene ether) and other homopolymers; 2, Copolymers such as copolymers of 6-dimethylphenol and other phenols (eg, 2,3,6-trimethylphenol or 2-methyl-6-butylphenol); and the like. Among them, poly(2,6-dimethyl-1,4-phenylene ether), 2,6- A copolymer of dimethylphenol and 2,3,6-trimethylphenol, more preferably poly(2,6-dimethyl-1,4-phenylene ether).

The aforementioned PPE can be produced by a known method. As the manufacturing method of PPE, for example, but not limited to: the oxidative polymerization of 2,6-xylenol by using a complex of cuprous salt and amine as a catalyst and described in the US Patent No. 3306874 specification proposed by Hay method; U.S. Patent No. 3306875 specification, U.S. Patent No. 3257357 specification, U.S. Patent No. 3257358 specification, Japanese Patent Publication No. 52-17880, Japanese Patent Application No. 50-51197, Japanese Patent Application No. 63-152628 The methods described in the Publication No. 1, etc.

The above-mentioned PPE may be a modified PPE obtained by reacting the above-mentioned homopolymer and/or the above-mentioned copolymer with a styrene-based monomer or a derivative thereof and/or an α,β-unsaturated carboxylic acid or a derivative thereof. Here, as the grafted or added amount of the above-mentioned styrene-based monomer or derivative thereof and/or α,β-unsaturated carboxylic acid or derivative thereof, relative to 100% by mass of component (a), preferably 0.01% by mass to 10% by mass.

As a method for producing the above-mentioned modified PPE, for example, the following method is mentioned: in the presence or absence of a radical generating agent, at a temperature of 80°C to 350°C in a molten state, a solution state, or a slurry state. make it react.

As the above-mentioned PPE, a mixture of the above-mentioned homopolymer and/or the above-mentioned copolymer and the above-mentioned modified PPE in any ratio can be used.

As polystyrene resin contained in (a) component, the polymer obtained by superposing|polymerizing the monomer component containing a styrene compound is mentioned. A compound copolymerizable with a styrene compound may be contained in the said monomer component.

The above-mentioned polystyrene resins may be used alone or in combination of two or more.

The polystyrene-based resin preferably contains more than 60% by mass of structural units derived from styrene-based compounds, more preferably 70% by mass or more, based on 100% by mass of the styrene-based resin.

Examples of the styrene-based compounds include, but are not limited to, styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, p-methylstyrene, p-tert-butylbenzene Ethylene, ethyl styrene, etc. In particular, styrene is preferably used from the viewpoint of raw material availability.

Examples of the polystyrene-based resin include atactic polystyrene, rubber-reinforced polystyrene (high-impact polystyrene, HIPS), and styrene-acrylonitrile copolymers with a styrene content of 50% by weight or more. (AS), and the styrene-acrylonitrile copolymer rubber-reinforced AS resin, etc., preferably random polystyrene and/or high-impact polystyrene.

As the component (a), polyphenylene ether composed of PPE and polystyrene resin and having a mass ratio of PPE to polystyrene resin (PPE/polystyrene resin) of 99/1 to 5/95 can be used. Department of resin. From the viewpoint of heat resistance and molding fluidity, the mass ratio of PPE to polystyrene resin (PPE/polystyrene resin) is preferably 90/10 to 10/90.

Regarding the content of component (a) in the resin composition of the present embodiment, from the viewpoint of workability, heat resistance, impact resistance, and vibration fatigue characteristics, the total amount of component (a) and component (b) When it is 100 mass parts, it is 40-99 mass parts, Preferably it is 40-98 mass parts, More preferably, it is 50-95 mass parts. When the content of the component (a) is in the range of 40 parts by mass to 99 parts by mass, the balance of workability, heat resistance, impact resistance, and vibration fatigue characteristics can be sufficiently improved.

It is preferable that content of the (a) component in the resin composition of this embodiment is 2 mass % - 98 mass % with respect to the resin composition whole quantity (100 mass %) from a flame-retardant viewpoint. Moreover, it is preferable that content of the PPE in the resin composition of this embodiment is 0.25 mass % - 92.2 mass % with respect to the resin composition whole quantity (100 mass %) from a flame retardancy point.

((b) inorganic filler)

As (b) the inorganic filler used in this embodiment, a fibrous inorganic filler, a sheet-like inorganic filler, etc. are mentioned, for example. The said inorganic filler may contain 0.1 mass % or more of white-type inorganic fillers (for example, the inorganic filler whose whiteness measured according to JISZ8715 is 70% or more). The above-mentioned inorganic fillers may be used alone or in combination of two or more.

In addition, the (c) titanium oxide, (d) calcium carbonate, (e) condensed phosphoric acid ester flame retardant, (f) elastomer mentioned later are not included in (b) component.

Examples of the fibrous inorganic filler include whiskers such as glass fibers, carbon fibers, silicone fibers, silica-alumina fibers, silicon nitride fibers, silicon carbide fibers, potassium titanate, and silicon nitride, Metal fibers such as wollastonite, aluminum, titanium, copper, etc.

The L/D represented by the ratio of the average fiber diameter (D) to the average length (L) of the fibrous inorganic filler is preferably 5 or more, more preferably 20 or more, from the viewpoint of its reinforcing effect. , is more preferably 100 or more, and is preferably 500 or less.

Examples of the flaky inorganic filler include metal foils such as glass flakes, mica, talc, and aluminum flakes.

R/H represented by the ratio of the average thickness (H) to the average plate diameter (R) of the above-mentioned sheet-like inorganic filler is preferably 5 or more, more preferably 10 or more, from the viewpoint of its reinforcing effect. More preferably, it is 20 or more, and preferably 3,000 or less.

As the inorganic filler, glass fibers, carbon fibers, glass flakes, mica, talc, and flake graphite are preferable from the viewpoint of obtaining more excellent processability, heat resistance, impact resistance, and vibration fatigue characteristics.

The above-mentioned inorganic filler may be subjected to surface treatment.

Examples of the surface treatment on the inorganic filler include surface treatment with various coupling agents such as silane-based or titanate-based coupling agents. Among these, surface treatment with aminosilane or epoxysilane is preferable from the viewpoint of adhesiveness with resin. Vibration fatigue characteristics and impact resistance strength can be further improved by bonding resin and inorganic filler.

As a method of surface-treating the inorganic filler, for example, when the inorganic filler is glass fiber, a method of immersing the fiber in a silane coupling agent solution and drying it when the fiber is drawn; Or in the case of a powder form, methods, such as the method of impregnating a silane coupling agent solution and drying it, are mentioned.

The content of the component (b) in the resin composition of the present embodiment is based on 100% of the total of the components (a) and (b) from the viewpoint of workability, heat resistance, impact resistance, and vibration fatigue characteristics. Parts by mass are 1 to 60 parts by mass, preferably 2 to 60 parts by mass, more preferably 5 to 50 parts by mass. When the content of the component (b) is in the range of 1 to 60 parts by mass, the balance of workability, heat resistance, impact resistance, and vibration fatigue characteristics can be sufficiently improved.

The total amount of the components (a) and (b) in the resin composition of the present embodiment is preferably 64.5% by mass to 99.6% by mass from the viewpoint of whiteness, workability, impact resistance, and vibration fatigue properties. , More preferably 80.0% by mass to 96.7% by mass.

((c) titanium oxide)

(c) Titanium oxide used in this embodiment is not particularly limited, and known titanium oxide can be used.

(c) The primary particle size of titanium oxide is preferably 0.01 μm to 0.5 μm, more preferably 0.05 μm to 0.4 μm, and still more preferably 0.15 μm to 0.3 μm.

In addition, the primary particle diameter can be measured based on JISZ8825.

(c) Titanium oxide can be surface-treated with hydrous oxides such as aluminum, magnesium, zirconia titanium, tin, and/or oxides, higher fatty acid salts such as stearic acid, and organosilicon compounds.

(c) Titanium oxide can be produced by a dry method or a wet method. In addition, the crystal structure of (c) titanium oxide may be any of rutile type and anatase type, but the rutile type is preferable from the viewpoint of the white colorability and thermal stability of the resin composition.

The compounding quantity of (c) titanium oxide is 0.1-5 mass parts with respect to the total 100 mass parts of (a) polyphenylene ether resin and (b) inorganic filler, Preferably it is 0.1-3 mass parts. parts by mass, more preferably 0.3 parts by mass to 3 parts by mass. When the (c) component is 0.1 mass part or more, the whiteness of a resin composition improves remarkably, and when (c) component is less than 5 mass parts, the fall of impact resistance can be suppressed.

((d) calcium carbonate)

The (d) calcium carbonate used in the present embodiment preferably has an average particle diameter within a range of 0.1 μm to 10 μm, more preferably 0.5 μm to 5 μm. It is preferable from the standpoint of the balance of dispersibility, white colorability, handleability at the time of manufacture, impact resistance, and vibration fatigue characteristics by making the average particle diameter into the said range.

The average particle diameter can be measured according to JIS Z8825, for example, using an electron microscope (JIS Z8827) or a laser diffraction particle size distribution analyzer.

(d) Calcium carbonate may be surface-treated.

The surface treatment for (d) calcium carbonate is not particularly limited, and examples thereof include surface treatment with fatty acids, resin acids, silicic acid, phosphoric acid, silane coupling agents, alkylarylsulfonic acids or salts thereof, etc. . Examples of the fatty acid include saturated or unsaturated fatty acids having 6 to 31 carbon atoms, preferably 12 to 28 carbon atoms. Among these, it is preferable to surface-treat with fatty acid from the viewpoint of dispersibility and handleability at the time of manufacture. In addition, when calcium carbonate surface-treated with a fatty acid is used as the component (d), the inorganic filler is more uniformly dispersed in the resin, and the vibration fatigue characteristics and impact resistance strength of the resin composition are further excellent.

The compounding quantity of (d) calcium carbonate is 0.3-10 mass parts with respect to the total 100 mass parts of (a) polyphenylene ether resin and (b) inorganic filler, Preferably it is 0.3-8 mass parts. parts by mass, more preferably 0.5 parts by mass to 7 parts by mass. When the (d) component is 0.3 mass parts or more, the whiteness of a resin composition improves remarkably, and when (d) component is 10 mass parts or less, the fall of impact resistance can be suppressed.

In the resin composition of the present embodiment, the mass ratio of the content of the component (b) to the total of the content of the component (c) and the content of the component (d) from the viewpoint of whiteness, impact resistance, and vibration fatigue characteristics (Inorganic filler/total amount of titanium oxide and calcium carbonate) is preferably 1/15 to 60/0.4, more preferably 1/10 to 60/0.8.

((e) Condensed phosphoric acid ester flame retardant)

The resin composition of the present embodiment may contain (e) a condensed phosphoric acid ester-based flame retardant. By including the component (e), the flame retardancy-promoting effect of the polyphenylene ether-based resin of the component (a) and the flame retardancy imparting effect of the component (e) complement each other, and contribute greatly to imparting flame retardancy to the resin composition of the present embodiment. big effect.

As said (e) condensed phosphoric acid ester flame retardant, for example, phosphoric acid ester represented by following formula (2) and/or its condensate can be used, but it is not limited.

【Chemical 2】

In formula (2), R ⁵ , R ⁶ , R ⁷ and R ⁸ each independently represent a group selected from a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl-substituted alkyl group, an aryl group, a halogen-substituted aryl group, and A monovalent group in the group consisting of alkyl substituting aryl. X represents an arylene group. n is an integer of 0-5.

In addition, when it is phosphoric acid ester and/or its condensate which said n differs, said n shows these average values. In the case of n=0, the compound of formula (2) represents a phosphate monomer.

Examples of typical phosphoric acid ester monomers include, but are not limited to, triphenyl phosphate, tricresyl phosphate, tris(xylyl) phosphate, and the like.

As a condensate of the said phosphoric acid ester, n can take the value of 1-5 on average normally, Preferably it is 1-3 on average.

In addition, from the viewpoint of flame retardancy and heat resistance exhibited when kneaded in other resins, at least one of the above-mentioned R ⁵ , R ⁶ , R ⁷ and R ⁸ is preferably an aryl group, more preferably all of them are aryl groups. base. Moreover, from the same point of view, phenyl, xylyl, tolyl or their halogenated derivatives are mentioned as a preferable aryl group.

Examples of the arylene group of the aforementioned X include residues obtained by removing two hydroxyl groups from resorcinol, hydroquinone, bisphenol A, bisphenol, or halogenated derivatives thereof, respectively.

Examples of the condensed phosphoric acid ester compound include, but are not limited to, resorcinol-bisphenyl phosphate compounds, bisphenol A-polyphenyl phosphate compounds, bisphenol A-polycresyl phosphate compounds, and the like.

Regarding the content of the (e) condensed phosphoric acid ester-based flame retardant in the resin composition of the present embodiment, when the total amount of the (a) component and (b) component is 100 parts by mass, from the perspective of fluidity and heat resistance From the viewpoint of property and flame retardancy, it is preferably 2 to 20 parts by mass, more preferably 3 to 20 parts by mass, and still more preferably 5 to 18 parts by mass. If the content of the component (e) is in the range of 2 parts by mass to 20 parts by mass, the balance of fluidity, heat resistance, and flame retardancy can be further improved sufficiently.

((f) Elastomer)

The resin composition of this embodiment may contain an elastomer as (f) component as needed.

As (f) component, block copolymers composed of at least two polymer blocks mainly composed of aromatic vinyl compounds and at least one polymer block mainly composed of conjugated diene compounds ( Hereinafter, it may be simply referred to as "block copolymer") and/or a hydrogenated product of the block copolymer. By containing these block copolymers, the resin composition of this embodiment has more excellent impact resistance.

When the component (f) contains a polymer containing a structural unit derived from a styrene compound, the polymer may contain a structural unit derived from a styrene compound in an amount of 60% or less with respect to 100% by mass of the polymer.

The term "mainly" in the polymer block mainly composed of an aromatic vinyl compound means that at least 50 mass% or more of the polymer block is derived from a structural unit derived from an aromatic vinyl compound. block. More preferably, it is 70 mass % or more, Still more preferably, it is 80 mass % or more, Most preferably, it is 90 mass % or more.

In addition, "mainly" in a polymer block mainly composed of a conjugated diene compound also means a block in which at least 50% by mass or more is a structural unit derived from a conjugated diene compound. More preferably, it is 70 mass % or more, Still more preferably, it is 80 mass % or more, Most preferably, it is 90 mass % or more.

For example, even in the case of a polymer block in which a small amount of structural units derived from other compounds such as a conjugated diene compound are randomly bonded to a polymer block mainly composed of an aromatic vinyl compound, as long as the polymerization If more than 50% by mass of the polymer block is formed by structural units derived from aromatic vinyl compounds, it is also considered as a block copolymer mainly composed of aromatic vinyl compounds. In addition, the same applies to the case of a polymer block mainly composed of a conjugated diene compound.

Examples of the aromatic vinyl compound include styrene, α-methylstyrene, vinyltoluene, and the like, and one or more compounds selected from these are used, among which styrene is preferred.

Examples of the conjugated diene compound include butadiene, isoprene, piperylene, and 1,3-pentadiene, and one or more compounds selected from these are used, among which butadiene is preferred. alkenes, isoprene, and combinations thereof.

In addition, the block copolymer is preferably a polymer block (I) mainly composed of an aromatic vinyl compound and a polymer block (II) mainly composed of a conjugated diene compound. Type, I-II-I-II type of bonded block copolymer. Among them, type I-II-I is more preferable.

The component (f) may be a mixture of the above block copolymers.

The aforementioned block copolymer is preferably a hydrogenated block copolymer. A hydrogenated block copolymer refers to an aliphatic block copolymer mainly composed of a conjugated diene compound by hydrogenating the block copolymer of the above-mentioned aromatic vinyl compound and a conjugated diene compound. The amount of double bonds (ie, hydrogenation rate) is controlled within a range of more than 0% and 100%. The hydrogenation rate of the hydrogenated block copolymer is preferably 50% or more, more preferably 80% or more, and most preferably 98% or more.

As the hydrogenated block copolymer in the present embodiment, conventionally known and sold hydrogenated block copolymers can be used, and any hydrogenated block copolymer can be used as long as it falls within this category.

As component (f), mixtures of non-hydrogenated block copolymers and hydrogenated block copolymers can also be used without problems.

In addition, as the component (f), a wholly or partially modified block copolymer described in WO 02/094936 A and a block copolymer in which oil is preliminarily mixed can also be used suitably.

Regarding the content of component (f) in the resin composition of the present embodiment, when the total amount of component (a) and component (b) is 100 parts by mass, the heat resistance, impact resistance and vibration fatigue characteristics From the point of view, it is preferably 1 to 20 parts by mass, more preferably 1 to 15 parts by mass, and even more preferably 2 to 15 parts by mass. When content of this (f) component is in the range of 1 mass part - 20 mass parts, the balance of heat resistance, impact resistance, and vibration fatigue characteristics can be made favorable enough.

(other ingredients)

In addition to the above-mentioned components, the resin composition of this embodiment may contain other components as needed within the range which does not impair the whiteness maintenance, impact resistance, and vibration fatigue characteristics of the resin composition.

Examples of the above-mentioned other components include, but are not limited to, thermoplastic elastomers (polyolefin-based elastomers), heat stabilizers, antioxidants, metal inertizers, crystal nucleating agents, flame retardants (not conforming to (e) component organic phosphate compounds, ammonium polyphosphate compounds, silicone flame retardants, etc.), plasticizers (low molecular weight polyethylene, epoxidized soybean oil, polyethylene glycol, fatty acid esters, etc.), weather resistance ( Light) properties improver, sliding agent, organic filler and reinforcing material (polyacrylonitrile fiber, aramid fiber, etc.), various colorants, anti-sticking agent, etc.

[Manufacturing method of resin composition]

The resin composition of this embodiment can be manufactured by melt-kneading the said (a)-(d) component, further if necessary, (e) component, (f) component, and other components.

The melt-kneading machine for melt-kneading is not limited to the following equipment, and examples include single-screw extruders, multi-screw extruders including twin-screw extruders, rolls, kneaders, Brabenders, etc. Heat-melting kneading machines such as plastometers and Banbury kneaders, especially twin-screw extruders are preferable from the viewpoint of kneading properties. Specifically, the ZSK series manufactured by COPERION, the TEM series manufactured by Toshiba Machine Co., Ltd., the TEX series manufactured by Nippon Steel Works Co., Ltd., etc. are mentioned.

A preferred production method using an extruder will be described below. The L/D (barrel effective length/barrel inner diameter) of the extruder is preferably in the range of 20 to 60, more preferably 30 to 50.

The structure of the extruder is not particularly limited. For example, it is preferable to provide a first raw material supply port on the upstream side in the flow direction of the raw material, and to provide a first vacuum exhaust port downstream of the first raw material supply port. A second raw material supply port is provided downstream of the exhaust port (the third and fourth raw material supply ports may be further provided if necessary), and a second vacuum exhaust port is further provided downstream of these raw material supply ports. In particular, it is more preferable to install a kneading section upstream of the first vacuum exhaust port, to install a kneading section between the first vacuum exhaust port and the second raw material supply port, and to install a kneading section between the second to fourth raw material supply ports and the second raw material supply port. A kneading section is provided between the vacuum vents.

The method of supplying the raw materials to the above-mentioned second to fourth raw material supply ports is not particularly limited, and compared with the simple addition and supply from the open ports of the second to fourth raw material supply ports of the extruder, the forced side feeder is used to feed the raw materials from the extruder The method of side opening supply tends to enable more stable supply, and is therefore preferable.

In particular, when the raw material contains powder and it is desired to reduce the generation of cross-linked products or carbides due to the thermal history of the resin, it is more preferable to use the method of using a forced side feeder fed from the side of the extruder, and further A method in which forced side feeders are provided at the second to fourth raw material supply ports and these raw material powders are separately supplied is preferred.

In addition, in the case of adding a liquid raw material, it is preferable to use a method of adding to an extruder using a plunger pump, a gear pump, or the like.

In addition, the upper openings of the second to fourth raw material supply ports of the extruder can also be used as openings for releasing the air conveyed together.

The melt-kneading temperature and the screw speed in the melt-kneading step of the resin composition are not particularly limited, and generally, in the case of a crystalline resin, one that can be smoothly processed by heating and melting at a temperature above the melting point of the crystalline resin can be selected. As for the temperature, in the case of an amorphous resin, it is possible to select a temperature that can be smoothly processed by heating and melting above its glass transition temperature, usually arbitrarily selected from 200°C to 370°C, and the screw speed is set at 100rpm to 1200rpm.

As one of the preferred specific methods of producing the resin composition of the present invention by using a twin-screw extruder, for example, the following method can be mentioned: (a) component polyphenylene ether resin, (c) component titanium oxide (d) component calcium carbonate and (f) component elastomer are supplied to the first supply port of the twin-screw extruder, and the heating and melting zone is set to the melting temperature of the polyphenylene ether resin at 100 rpm to 1200 rpm, preferably Melt and knead at a screw speed of 200rpm to 500rpm, and supply (a) component, (c) component, (d) component and (f) component from the second supply port of the twin-screw extruder in the state of melt kneading The (e) component condensed phosphoric acid ester-based flame retardant was supplied from the third supply port with the (b) component inorganic filler, and further melt-kneaded. In addition, as to the position where the (a) component, (c) component, (d) component, and (f) component are supplied to the twin-screw extruder, they may be supplied collectively from the first supply port of the extruder as described above. , It is also possible to provide a second supply port, a third supply port, and a fourth supply port to supply each component separately.

In addition, in the case of reducing the generation of cross-linked products or carbides due to the thermal history of the resin in the presence of oxygen, it is preferable to keep the oxygen concentration of each process line in the path where each raw material is added to the extruder at Less than 1.0% by volume. The adding route is not particularly limited, and specific examples include piping, a gravimetric feeder with a replenishment tank, piping, a hopper, and a twin-screw extruder in order from the storage tank. The method for maintaining the low oxygen concentration as described above is not particularly limited, and a method of introducing an inert gas into each process pipeline with improved airtightness is effective. Usually, it is preferable to introduce nitrogen gas to maintain the oxygen concentration at less than 1.0% by volume.

Regarding the above-mentioned method for producing the resin composition, when (a) component polyphenylene ether-based resin or (f) component elastomer contains a powdery (volume average particle diameter of less than 10 μm) component, a twin-screw extruder is used When the resin composition of this embodiment is produced, the effect of further reducing the residue on the screw of the twin-screw extruder can be brought about, and for the resin composition obtained by the above-mentioned production method, it can bring about the reduction of black spots and foreign substances. Or the effect of carbides, etc.

As a specific manufacturing method of the resin composition of this embodiment, it is preferable to use an extruder which controls the oxygen concentration of each raw material supply port to less than 1.0 volume, and to implement any one of the following 1-3 methods.

1. The production method is as follows: the entire amount or part of (a) component, (c) component, (d) component and (f) component contained in the resin composition of the present embodiment, and a part of (b) component if necessary The components are melt-kneaded (first kneading step), and the remaining amount of (a) component, (c) component, (d) component and ( The f) component and the entire amount of (e) component are melt-kneaded (second kneading step), and the whole amount or a part of (b) is supplied to the kneaded product in a molten state obtained in the second kneading step. Components were melt-kneaded (third kneading step).

2. The production method is as follows: Melt-kneading (first kneading process) the entire amount of (a) component, (e) component, and (f) component contained in the resin composition of the present embodiment, cooling once and pelletizing After conversion, the other (b) component, (c) component, and (d) component are supplied and melt-kneaded in full amount (second kneading process).

3. The method of melt-kneading all the components (a)-(f) contained in the resin composition of this embodiment.

In particular, polyphenylene ether as a raw material of component (a) and hydrogenated block copolymer of component (f) with certain molecular structures are in the form of powder, and component (e) may be liquid, so the The bite property is poor, and it is difficult to increase the throughput per unit time. Furthermore, since the residence time of the resin in the extruder becomes longer, thermal deterioration tends to occur. In summary, the resin composition obtained by the production method of 1 or 2 above has excellent miscibility of each component compared with the resin composition obtained by the production method of 3, and can reduce cross-linked products or generation of carbides, and can increase the throughput of the resin per unit time, and can obtain a resin composition with excellent productivity and quality, so it is more preferable.

Here, in the above-mentioned first kneading step to the second kneading step, the kneaded product may be in a molten state, and the (a) component may be melted and pelletized once to avoid melting it again.

[molded product]

The molded article of the resin composition of the present embodiment can be used as an optical device mechanism part, a light source lamp peripheral part, a sheet or film for a metal film laminated substrate, a hard disk internal part, an optical fiber connector ferrule, a printer part, a copier part, an automobile Widely used in molded products such as automotive engine compartment parts such as radiator tank parts, and automotive lamp parts.

Example

The present invention will be described below with reference to specific examples and comparative examples, but the present embodiment is not limited thereto.

The measurement methods of the physical properties used in Examples and Comparative Examples are as follows.

((1) Charpy impact test)

According to the method described in ISO 179, the Charpy impact strength (kJ/m ² ) was measured. The higher the value, the more excellent the impact resistance is evaluated.

((2) Vibration fatigue test)

In accordance with JIS K7118 and K7119, using a hydraulic servo fatigue testing machine (manufactured by Saginomiya Co., Ltd., EHF-50-10-3), a tensile load (50 MPa) was applied with a sinusoidal wave at a frequency of 30 Hz in an atmosphere of 23 ° C. ), to find the vibration times of fracture. The greater the number of vibrations until fracture, the more excellent the vibration fatigue resistance was evaluated.

((3) Whiteness)

According to JIS Z8715, L value was calculated|required using the color-difference meter (Nippon Denshoku Kogyo Co., Ltd. ZE-2000). The higher the L value, the higher the evaluation whiteness.

((4) flame retardancy)

The test was carried out in accordance with the vertical burning test method of UL94 (the standard stipulated by Underwriters Laboratories).

Raw materials used in Examples and Comparative Examples are as follows.

<(a) Polyphenylene ether resin>

(a1): PPE (polyphenylene ether)

Polyphenylene ether obtained by oxidatively polymerizing 2,6-xylenol (reduced viscosity measured at 30° C. in a chloroform solution having a concentration of 0.5 g/dL: 0.51 dL/g).

(a2): High-impact polystyrene (trade name "POLYSTYRENE H9405", manufactured by PS Japan Corporation).

<(b) Inorganic filler>

(b1) The average diameter is 13 μm, and the average length is 3,000 μm. Glass fiber surface-treated with an aminosilane-based coupling agent.

(b2) The average diameter is 6 μm, and the average length is 3,000 μm. Carbon fiber surface-treated with an epoxy silane-based coupling agent.

(b3) The average sheet diameter is 130 μm, and the average thickness is 5 μm. Glass flakes surface-treated with an aminosilane-based coupling agent.

(b4) Talc (trade name "High Toron A", manufactured by Takehara Chemical Industry Co., Ltd.) with an average particle diameter of 3 μm.

(b5) Carbon black (trade name "#980", manufactured by Mitsubishi Chemical Corporation).

<(c)Titanium oxide>

(c1) Titanium oxide (primary particle diameter: 0.3 μm, trade name “RTC-30”, manufactured by Huntsman (UK) Co., Ltd.).

<(d) calcium carbonate>

(d1) Calcium carbonate having an average particle diameter of 12 μm.

(d2) Calcium carbonate (trade name "SUN LIGHT SL-100", manufactured by Takehara Chemical Industry Co., Ltd.) with an average particle diameter of 6 µm.

(d3) Calcium carbonate (trade name "SUN LIGHT SL-2200", manufactured by Takehara Chemical Industry Co., Ltd.) with an average particle diameter of 1.3 µm.

(d4) Calcium carbonate (trade name "NEOLIGHT SP", manufactured by Takehara Chemical Industry Co., Ltd.) with an average particle diameter of 0.08 μm.

<(e) Condensed phosphoric acid ester flame retardant>

(e1) Aromatic condensed phosphoric acid ester (trade name "CR-741", manufactured by Daihachi Chemical Industry Co., Ltd.).

<(f)Elastomer>

(f1) Synthesized polystyrene-hydrogenated polybutadiene-polystyrene structure, bound styrene content 33%, number average molecular weight 246,000, molecular weight distribution 1.07, hydrogenated polybutadiene part A hydrogenated block copolymer with a yield of 99.8%.

(f2) A block copolymer having a polystyrene-polybutadiene-polystyrene structure, a bound styrene content of 40%, a number average molecular weight of 90,000, and a molecular weight distribution of 1.17 was synthesized.

[Examples 1-13], [Comparative Examples 1-6]

The resin composition was produced using a twin-screw extruder ZSK-40 (manufactured by WERNER & PFLEIDERER). In this twin-screw extruder, a first raw material supply port is provided on the upstream side in the flow direction of the raw material, and a first vacuum exhaust port, a second raw material supply port, and a third raw material supply port are provided downstream of the first raw material supply port. The raw material supply port, and further, a second vacuum exhaust port is provided downstream of them. The second raw material supply port is fed from the top opening of the extruder using a gear pump.

Using the extruder set as above, add (a) component, (c) component, (d) component, and (f) component from the first raw material supply port with the composition shown above, and add ( e) Condensed phosphoric acid ester-based flame retardant, add (b) inorganic filler from the third raw material supply port, melt and knead under the conditions of extrusion temperature 240°C to 310°C, screw rotation speed 300rpm, discharge rate 100kg/hour, and manufacture Out of particles. In addition, (b4), (b5) component in (b) component is added from the 1st raw material supply port.

Pellets of this resin composition are used to supply to a coaxial screw type injection molding machine set at 250°C to 310°C, and molded products for ASTM type 1 vibration fatigue measurement are obtained under injection molding conditions with a mold temperature of 60°C to 120°C . The molded article obtained here was left to stand under the conditions of 23° C. and a relative humidity of 50% for 24 hours or more, and (2) vibration fatigue test and (3) measurement of whiteness were performed.

In addition, the test piece type A was molded according to ISO 10724-1 under the same injection molding conditions as above. (1) Charpy impact strength (ISO 179) was measured using this sample.

In addition, a test piece having a length of 127 mm, a width of 12.7 mm, and a thickness of 1.6 mm was molded under the same injection molding conditions as above. Using this test piece, a vertical burning test based on UL94 was performed, and (4) flame retardancy was evaluated.

These results are collectively described in Tables 1-2.

As shown in Tables 1-2, it turned out that the resin composition of Examples 1-13 was excellent in impact resistance and vibration fatigue characteristics, and also was excellent in whiteness.

Comparative Examples 1 to 6 were inferior to the Examples in the results of any one or more of impact resistance, vibration fatigue characteristics, and whiteness.

Industrial Applicability

The molded article molded from the resin composition of the present embodiment has excellent white colorability, and is excellent in impact resistance and vibration fatigue characteristics, so that the degree of freedom in design of the resin molded article can be increased. Therefore, it can be used as various components in electrical/electronic equipment, automotive equipment, chemical equipment, and optical equipment, such as chassis or housings for multi-function digital discs, etc., optical equipment mechanism components such as optical pickup slide bases, and light sources. Lamp peripheral parts, sheets or films for metal film laminated substrates, internal parts of hard disks, connector ferrules for optical fibers, internal parts of laser beam printers (toner cartridges, etc.), internal parts of inkjet printers, internal parts of copiers, car radiators It is industrially applicable to car engine compartment parts such as water tank parts and car lamp parts.

Claims (7)

1. A resin composition, characterized in that, Contains: (a) 40 to 99 parts by mass of polyphenylene ether resin, (b) 1 to 60 parts by mass of inorganic filler, (c) 0.1 to 5 parts by mass of titanium oxide, (d) 0.3 mass parts - 10 mass parts of calcium carbonate. 2. The resin composition according to claim 1, wherein (d) calcium carbonate has an average particle diameter of 0.1 μm to 10 μm. 3. resin composition as claimed in claim 1 or 2, wherein, (a) polyphenylene ether-based resins include polyphenylene ether and polystyrene-based resins, The mass ratio of the polyphenylene ether to the polystyrene resin, that is, polyphenylene ether/polystyrene resin, is 99/1 to 5/95. 4. The resin composition according to claim 3, wherein the polystyrene resin is atactic polystyrene and/or high-impact polystyrene. 5. The resin composition according to any one of claims 1 to 4, wherein (e) condensed phosphoric acid is contained with respect to a total of 100 parts by mass of (a) polyphenylene ether resin and (b) inorganic filler 2 to 20 parts by mass of the ester-based flame retardant. 6. The resin composition according to any one of claims 1 to 5, wherein (f) elastomer is contained with respect to 100 parts by mass of the total of (a) polyphenylene ether resin and (b) inorganic filler 1 to 20 parts by mass. 7. The resin composition according to claim 6, wherein the (f) elastomer is a block copolymer and/or a hydrogenated block copolymer.