JP6827783B2 - Resin composition - Google Patents

Description

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

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

In recent years, there has been a strong demand for improved fluidity and impact resistance during heat melting processing in order to reduce the size and weight of resin parts. However, in the polyphenylene ether-based resin to which an inorganic filler material is added, which is colored white, there is a problem that the impact resistance and the vibration fatigue characteristics are remarkably lowered.
For this reason, many improvements have been proposed using elastomers in terms of materials. However, the white-colored inorganic filler-added resin composition is not practical because the impact resistance imparting effect due to the addition of the elastomer is small.

In addition, it is not possible to stop the white coloring from the viewpoint of design and prevention of assembly mistakes.
At present, no specific solution to this problem has been disclosed, and an improved resin composition is desired.

An object of the present invention is to provide a resin composition having excellent impact resistance and vibration fatigue characteristics while maintaining whiteness.

As a result of diligent studies to solve the above problems, the present invention provides a resin composition containing a specific amount of a polyphenylene ether-based resin, an inorganic filler, titanium oxide, and calcium carbonate, which has good whiteness while maintaining good whiteness. We have found that impact resistance and vibration fatigue characteristics can be obtained, and have arrived at the present invention.

That is, the present invention is as follows.
[1]
For a total of 100 parts by mass of (a) polyphenylene ether-based resin and (b) inorganic filler
(A) 40 to 99 parts by mass of polyphenylene ether resin,
(B) 1 to 60 parts by mass of the inorganic filler,
(C) Titanium oxide in an amount of 0.1 to 5 parts by mass,
(D) Contains 0.3 to 10 parts by mass of calcium carbonate
The inorganic filler (b) is made of glass fiber, carbon fiber, silicone fiber, silica / alumina fiber, silicon nitride fiber, silicon carbide fiber, potassium titanate whisker , silicon nitride whisker, wallastnite fiber , or aluminum . fibers, fibers of titanium, copper fibers, glass flakes, mica, and at least one der selected from the group consisting of aluminum flakes is,
The average particle diameter of the (d) calcium carbonate Ru 0.5~6μm der,
A resin composition characterized by the above.
[2]
The inorganic filler (b) is made of glass fiber, carbon fiber, silicone fiber, silica / alumina fiber, silicon nitride fiber, silicon carbide fiber, potassium titanate whisker , silicon nitride whisker, wallastnite fiber , or aluminum . It is at least one selected from the group consisting of fibers , titanium fibers , and copper fibers , and is represented by (b) the ratio of the average diameter (D) to the average length (L) of the inorganic filler. The resin composition according to [1], wherein is 5 or more and 500 or less.
[3]
The (b) inorganic filler is at least one selected from the group consisting of flake-shaped glass, mica, and aluminum flakes, and has the average thickness (H) and average plate diameter (R) of the (b) inorganic filler. The resin composition according to [1], wherein the R / H represented by the ratio is 5 or more and 3000 or less.

[4]
(A) The polyphenylene ether-based resin contains polyphenylene ether and a polystyrene-based resin.
The resin composition according to any one of [1] to [3] , wherein the mass ratio (polyphenylene ether / polystyrene resin) of the polyphenylene ether to the polystyrene resin is 99/1 to 5/95.

[5]
The resin composition according to [4] , wherein the polystyrene-based resin is atactic polystyrene and / or high-impact polystyrene.

[6]
Any of [1] to [5] containing 2 to 20 parts by mass of (e) condensed phosphoric acid ester flame retardant with respect to 100 parts by mass of the total of (a) polyphenylene ether-based resin and (b) inorganic filler. The resin composition according to.

[7]
The resin composition according to any one of [1] to [6] , which contains 1 to 20 parts by mass of (f) an elastomer with respect to a total of 100 parts by mass of (a) a polyphenylene ether-based resin and (b) an inorganic filler. ..

[8]
(F) The resin composition according to [7] , wherein the elastomer is a block copolymer and / or a hydrogenated block copolymer.

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

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

[Resin composition]
The resin composition of the present embodiment is (a) a polyphenylene ether-based resin (in this specification, it may be referred to as "(a) component"), (b) an inorganic filler (in this specification, "" It may be referred to as "(b) component"), (c) titanium oxide (sometimes referred to as "(c) component" in the present specification), and (d) calcium carbonate (this specification). In the above, "(d) component" may be described, and the content of the component (a) is 40 to 99 parts by mass with respect to a total of 100 parts by mass of the component (a) and the component (b). The content of the component (b) is 1 to 60 parts by mass, the content of the component (c) is 0.1 to 5 parts by mass, and the content of the component (d) is 0.3 to 10 parts by mass.
Since it is configured in this way, the resin composition of the present embodiment can exhibit excellent impact resistance and vibration fatigue characteristics while maintaining whiteness.

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

((A) Polyphenylene ether-based resin)
Since the resin composition of the present embodiment contains (a) a polyphenylene ether-based resin (sometimes simply referred to as "PPE-based resin" in the present specification), it is excellent in flame retardancy and heat resistance.

The PPE-based resin preferably contains a polyphenylene ether (sometimes referred to as “PPE” in the present specification) and a polystyrene-based resin, and may be a mixed resin composed of PPE and a polystyrene-based resin. However, it may be a resin composed only of PPE.
Since the PPE-based resin contains PPE, the resin composition of the present embodiment is further excellent in flame retardancy and heat resistance.

上記式（１）中、Ｒ^１、Ｒ^２、Ｒ^３、及びＲ^４は、各々独立して、水素原子、ハロゲン原子、炭素数１〜７の第１級アルキル基、炭素数１〜７の第２級アルキル基、フェニル基、ハロアルキル基、アミノアルキル基、炭化水素オキシ基、及び少なくとも２個の炭素原子がハロゲン原子と酸素原子とを隔てているハロ炭化水素オキシ基からなる群から選択される一価の基である。 Examples of the PPE include a homopolymer having a repeating unit structure represented by the following formula (1) and a copolymer having a repeating unit structure represented by the following formula (1).
The PPE may be used alone or in combination of two or more.

In the above formula (1), R ¹ , R ² , R ³ , and R ⁴ independently have a hydrogen atom, a halogen atom, a primary alkyl group having 1 to 7 carbon atoms, and 1 to 7 carbon atoms. Selected from the group consisting of a secondary alkyl group, a phenyl group, a haloalkyl group, an aminoalkyl group, a hydrocarbon oxy group, and a halo hydrocarbon oxy group in which at least two carbon atoms separate the halogen atom from the oxygen atom. It is the basis of the monovalent value.

From the viewpoint of fluidity, toughness and chemical resistance during processing, the PPE has a reduced viscosity measured with an Ubbelohde viscous tube under the condition of 30 ° C. using a chloroform solution having a concentration of 0.5 g / dL. It is preferably 0.15 to 2.0 dL / g, more preferably 0.25 to 1.0 dL / g, and even more preferably 0.30 to 0.70 dL / g.

The PPE is not limited to the following, but is, for example, poly (2,6-dimethyl-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; 2,6-dimethylphenol and other phenols Examples include polymers such as copolymers with the same class (eg, 2,3,6-trimethylphenol and 2-methyl-6-butylphenol); and the like. Among them, poly (2,6-dimethyl-1,4-phenylene ether) and 2,6-dimethylphenol are used from the viewpoint of the balance between toughness and rigidity when made into a resin composition and the availability of raw materials. A copolymer with 2,3,6-trimethylphenol is preferable, and poly (2,6-dimethyl-1,4-phenylene ether) is more preferable.

The PPE can be produced by a known method. The method for producing PPE is not limited to the following, but for example, 2,6-xylenol is used as a catalyst using a complex of ferrous salt and amine by Hay described in US Pat. No. 3,306,874. Method of oxidative polymerization, US Pat. No. 3,306,875, US Pat. No. 3,257,357, US Pat. No. 3,257,358, Japanese Patent Application Laid-Open No. 52-17880, Japanese Patent Application Laid-Open No. 50-51197, Japanese Patent Application Laid-Open No. 63 Examples thereof include the methods described in JP-A-152628.

The PPE is a modified PPE obtained by reacting the homopolymer and / or the copolymer with a styrene-based monomer or a derivative thereof, and / or an α, β-unsaturated carboxylic acid or a derivative thereof. There may be. Here, the amount of graft or addition of the styrene-based monomer or its derivative and / or α, β-unsaturated carboxylic acid or its derivative is 0.01 to 10% by mass with respect to 100% by mass of the component (a). It is preferably%.

Examples of the method for producing the modified PPE include a method of reacting in the presence or absence of a radical generator in a molten state, a solution state or a slurry state at a temperature of 80 to 350 ° C.
As the PPE, a mixture of the homopolymer and / or the copolymer and the modified PPE in an arbitrary ratio may be used.

Examples of the polystyrene-based resin contained in the component (a) include a polymer obtained by polymerizing a monomer component containing a styrene-based compound. The monomer component may contain a compound copolymerizable with the styrene compound.
The polystyrene-based resin 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 the styrene-based compound with respect to 100% by mass of the styrene-based resin, and more preferably 70% by mass or more.

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

Examples of the polystyrene-based resin include polystyrene, rubber-reinforced polystyrene (high-impact polystyrene, HIPS), styrene-acrylonitrile copolymer (AS) having a styrene content of 50% by weight or more, and the styrene-acrylonitrile co-weight. Examples thereof include AS resin in which the coalescence is rubber-reinforced, and atactic polystyrene and / or high-impact polystyrene are preferable.

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

The content of the component (a) in the resin composition of the present embodiment is 100 parts by mass based on the total amount of the component (a) and the component (b) from the viewpoint of processability, heat resistance, impact resistance and vibration fatigue characteristics. When it is, it is 40 to 99 parts by mass, preferably 40 to 98 parts by mass, and more preferably 50 to 95 parts by mass. When the content of the component (a) is in the range of 40 to 99 parts by mass, the balance between workability, heat resistance, impact resistance and vibration fatigue characteristics can be sufficiently good.

From the viewpoint of flame retardancy, the content of the component (a) in the resin composition of the present embodiment is preferably 2 to 98% by mass with respect to the total amount (100% by mass) of the resin composition. Further, the content of PPE in the resin composition of the present embodiment is 0.25 to 92.2% by mass with respect to the total amount (100% by mass) of the resin composition from the viewpoint of flame retardancy. preferable.

((B) Inorganic filler)
Examples of the (b) inorganic filler used in the present embodiment include a fibrous inorganic filler and a plate-shaped inorganic filler. The inorganic filler may contain 0.1% by mass or more of a white-based inorganic filler (for example, an inorganic filler having a whiteness of 70% or more as measured according to JIS Z8715). The above-mentioned inorganic filler may be used alone or in combination of two or more.
It is assumed that the component (b) does not include (c) titanium oxide, (d) calcium carbonate, (e) condensed phosphoric acid ester flame retardant, and (f) elastomer, which will be described later.

Examples of the fibrous inorganic filler include glass fibers, carbon fibers, silicone fibers, silica / alumina fibers, silicon nitride fibers, silicon carbide fibers, potassium titanate, whiskers such as silicon nitride, wallastnite, and aluminum. , Metal fibers such as titanium and copper.
The L / D represented by the ratio of the average diameter (D) and the average length (L) of the fibers of the fibrous inorganic filler is preferably 5 or more, preferably 20 or more, from the viewpoint of the reinforcing effect. It is more preferably 100 or more, and more preferably 500 or less.

Examples of the plate-shaped inorganic filler include metal foils such as flake-shaped glass, mica, talc, and aluminum flakes.
The R / H represented by the ratio of the average thickness (H) and the average plate diameter (R) of the plate-shaped inorganic filler is preferably 5 or more, preferably 10 or more, from the viewpoint of its reinforcing effect. More preferably, it is more preferably 20 or more, and more preferably 3000 or less.

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

The inorganic filler may be surface-treated.
Examples of the surface treatment for the inorganic filler include surface treatment with various coupling agents such as silane type and titanate type. Of these, surface treatment with aminosilane or epoxysilane is preferable from the viewpoint of adhesion to the resin. The adhesion between the resin and the inorganic filler further improves the vibration fatigue characteristics and the impact resistance.
As a method of surface treatment for the inorganic filler, for example, in the case of glass fiber, it is dipped in a silane coupling agent solution at the time of fiber collection and dried, and in the case of short fiber or powder, it is impregnated with a silane coupling agent solution and dried. Etc. can be mentioned.

The content of the component (b) in the resin composition of the present embodiment is based on 100 parts by mass of the total of the components (a) and (b) from the viewpoints of processability, heat resistance, impact resistance, and vibration fatigue characteristics. It is 1 to 60 parts by mass, preferably 2 to 60 parts by mass, and 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 between workability, heat resistance, impact resistance and vibration fatigue characteristics can be sufficiently good.

The total amount of the component (a) and the component (b) in the resin composition of the present embodiment is 64.5 to 99.6% by mass from the viewpoint of whiteness, processability, impact resistance, and vibration fatigue characteristics. Is preferable, and more preferably 80.0 to 96.7% by mass.

((C) Titanium oxide)
The titanium oxide (c) used in the present embodiment is not particularly limited, and known titanium oxide can be used.

(C) The primary particle size of titanium oxide is preferably 0.01 to 0.5 μm, more preferably 0.05 to 0, from the viewpoint of the balance between dispersibility, white colorability and handleability during production. It is .4 μm, more preferably 0.15 to 0.3 μm.
The primary particle size can be measured by JIS Z8825.

(C) Titanium oxide may be surface-treated with a hydrous oxide such as aluminum, magnesium, zirconia titanium, tin, and / or an oxide, a higher fatty acid salt such as stearic acid, and a surface treatment agent such as an organic silicon compound. ..

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

The blending amount of (c) titanium oxide is 0.1 to 5 parts by mass, preferably 0.1 to 3 parts by mass, based on 100 parts by mass of the total of (a) polyphenylene ether-based resin and (b) inorganic filler. It is by mass, more preferably 0.3 to 3 parts by mass. When the component (c) is 0.1 parts by mass or more, the whiteness of the resin composition is remarkably improved, and when it is less than 5 parts by mass, a decrease in impact resistance can be suppressed.

((D) Calcium carbonate)
The average particle size of (d) calcium carbonate used in the present embodiment is preferably in the range of 0.1 to 10 μm, more preferably 0.5 to 5 μm. When the average particle size is in the above range, it is preferable in terms of the balance between dispersibility, white colorability, handleability during manufacturing, impact resistance, and vibration fatigue characteristics.
The average particle size can be measured according to JIS Z8825 by, for example, an electron microscope (JIS Z8827) or a laser diffraction type particle size distribution measuring device.

(D) Calcium carbonate may be surface-treated.
(D) The surface treatment for calcium carbonate is not particularly limited, and examples thereof include surface treatment with fatty acids, resin acids, silicic acids, phosphoric acids, silane coupling agents, alkylarylsulfonic acids, salts thereof, and the like. Be done. Examples of the fatty acid include saturated or unsaturated fatty acids having 6 to 31 carbon atoms, preferably 12 to 28 carbon atoms. Of these, those that have been surface-treated with fatty acids are preferable from the viewpoint of dispersibility and handleability during production. Further, when calcium carbonate surface-treated with 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 of the resin composition are further excellent.

The amount of (d) calcium carbonate blended is 0.3 to 10 parts by mass, preferably 0.3 to 8 parts by mass, based on 100 parts by mass of the total of (a) polyphenylene ether-based resin and (b) inorganic filler. It is by mass, more preferably 0.5 to 7 parts by mass. When the component (d) is 0.3 parts by mass or more, the whiteness of the resin composition is remarkably improved, and when the component is 10 parts by mass or less, a decrease in 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 amount of the content of the component (c) and the content of the component (d) (inorganic filler / titanium oxide and calcium carbonate). From the viewpoint of whiteness, impact resistance, and vibration fatigue characteristics, the total amount) is preferably 1/15 to 60 / 0.4, and more preferably 1/10 to 60 / 0.8.

((E) Condensed Phosphate Ester Flame Retardant)
The resin composition of the present embodiment may contain (e) a condensed phosphoric acid ester flame retardant. By including the component (e), the flame-retardant effect of the polyphenylene ether-based resin of the component (a) and the flame-retardant effect of the component (e) are combined to impart flame retardancy to the resin composition of the present embodiment. Has a great effect on.

式（２）中、Ｒ^５、Ｒ^６、Ｒ^７及びＲ^８は、それぞれ独立して、水素原子、ハロゲン原子、アルキル基、シクロアルキル基、アリール置換アルキル基、アリール基、ハロゲン置換アリール基、及びアルキル置換アリール基からなる群より選ばれる一価の基を表す。Ｘは、アリーレン基を表す。ｎは、０〜５の整数である。
なお、上記ｎが異なるリン酸エステル及び／又はその縮合物である場合、上記ｎはそれらの平均値を表す。ｎ＝０である場合は、式（２）の化合物は、リン酸エステル単量体を示す。 The (e) condensed phosphoric acid ester-based flame retardant is not limited to the following, and for example, a phosphoric acid ester represented by the following formula (2) and / or a condensate thereof can be used.

In formula (2), R ⁵ , R ⁶ , R ⁷ and R ⁸ are independently hydrogen atoms, halogen atoms, alkyl groups, cycloalkyl groups, aryl-substituted alkyl groups, aryl groups, halogen-substituted aryl groups, respectively. And represents a monovalent group selected from the group consisting of alkyl-substituted aryl groups. X represents an arylene group. n is an integer from 0 to 5.
When the above n is a different phosphate ester and / or a condensate thereof, the above n represents an average value thereof. When n = 0, the compound of formula (2) represents a phosphate ester monomer.

Typical phosphate ester monomers include, but are not limited to, triphenylphosphine, tricresyl phosphate, trixylenyl phosphate and the like.

As the condensate of the phosphoric acid ester, n can usually take an average value of 1 to 5, but is preferably an average value of 1 to 3.

From the viewpoint of flame retardancy and heat resistance, which is expressed upon kneading with other resins, the R ^5, R ^6, R ⁷ and R ⁸ is preferably at least one is an aryl group, all It is more preferably an aryl group. From the same viewpoint, preferred aryl groups include phenyl, xylenyl, cresyl and halogenated derivatives thereof.

Examples of the arylene group of X include residues in which two hydroxyl groups are eliminated from resorcinol, hydroquinone, bisphenol A, biphenol, or halogenated derivatives thereof.

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

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

((F) Elastomer)
If necessary, the resin composition of the present embodiment may contain an elastomer as the component (f).
As the component (f), a block copolymer composed of a polymer block mainly composed of at least two aromatic vinyl compounds and a polymer block mainly composed of at least one conjugated diene compound (hereinafter, simply "block"). It may be described as "copolymer") and / or hydrogenated additives of block copolymers. By containing these block copolymers, the resin composition of the present embodiment has even better impact resistance.
When the component (f) contains a polymer containing a structural unit derived from a styrene compound, the polymer contains 60% or less of a structural unit derived from the styrene compound with respect to 100% by mass of the polymer. May be good.

As used herein, the term "mainly" in a polymer block mainly composed of an aromatic vinyl compound refers to a block in which at least 50% by mass or more is a constituent unit derived from an aromatic vinyl compound. It is more preferably 70% by mass or more, further preferably 80% by mass or more, and most preferably 90% by mass or more.
The same applies to "mainly" in a polymer block containing a conjugated diene compound as a main component, and refers to a block in which at least 50% by mass or more is a structural unit derived from the conjugated diene compound. It is more preferably 70% by mass or more, further preferably 80% by mass or more, and most preferably 90% by mass or more.
For example, even in the case of a polymer block in which structural units derived from other compounds such as a small amount of conjugated diene compound are randomly bonded to a polymer block mainly composed of an aromatic vinyl compound, the weight thereof. If 50% by mass or more of the coalesced block is formed from a structural unit derived from an aromatic vinyl compound, it is considered to be a block copolymer mainly composed of an aromatic vinyl compound. 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, and styrene is preferable.

Examples of the conjugated diene compound include butadiene, isoprene, piperylene, 1,3-pentadiene and the like, and one or more compounds selected from these are used. Among them, butadiene, isoprene and a combination thereof are preferable.

Further, as the block copolymer, the polymer block (I) mainly composed of an aromatic vinyl compound and the polymer block (II) mainly composed of a conjugated diene compound are classified into I-II-I type and I-II. It is preferable that it is a block copolymer having a bonding form selected from -I-II type. Of these, type I-II-I is more preferable.
The component (f) may be a mixture of the block copolymers.

The block copolymer is preferably a hydrogenated block copolymer. The hydrogenated block copolymer is an aliphatic double layer of a polymer block mainly composed of a conjugated diene compound by hydrogenating a block copolymer of the above-mentioned aromatic vinyl compound and a conjugated diene compound. The amount of bonds (that is, the hydrogenation rate) is controlled in the range of 100% over 0%. The hydrogenation rate of the hydrogenated block copolymer is preferably 50% or more, more preferably 80% or more, and most preferably 98% or more.

The hydrogenated block copolymer in the present embodiment is a conventionally known and commercially available hydrogenated block copolymer, and any hydrogenated block copolymer belonging to this category can be used.

As the component (f), a mixture of a non-hydrogenated block copolymer and a hydrogenated block copolymer can also be used without any problem.

In addition, as the component (f), a block copolymer in which all or part of the modification is performed, as described in International Publication No. 02/0994936, or a block copolymer in which oil is mixed in advance is also used. It can be suitably used.

The content of the component (f) in the resin composition of the present embodiment is from the viewpoint of heat resistance, impact resistance and vibration fatigue characteristics when the total amount of the components (a) and (b) is 100 parts by mass. Therefore, it is preferably 1 to 20 parts by mass, more preferably 1 to 15 parts by mass, and further preferably 2 to 15 parts by mass. When the content of the component (f) is in the range of 1 to 20 parts by mass, the balance between heat resistance, impact resistance and vibration fatigue characteristics can be sufficiently good.

(Other ingredients)
In addition to the above-mentioned components, the resin composition of the present embodiment contains other components as necessary within a range that does not impair the maintenance of whiteness, impact resistance, and vibration fatigue characteristics of the resin composition. May be good.

The other components are not limited to the following, but are, for example, thermoplastic elastomers (polyolefin-based elastomers), heat stabilizers, antioxidants, metal inactivating agents, crystal nucleating agents, and flame retardants ((() e) Organic phosphate ester compounds, ammonium polyphosphate compounds, silicone flame retardants, etc. that do not correspond to the components), plasticizers (low molecular weight polyethylene, epoxidized soybean oil, polyethylene glycol, fatty acid esters, etc.), weather resistance (light) ) Sex improvers, slip agents, organic fillers and reinforcing materials (polyacrylonitrile fibers, aramid fibers, etc.), various colorants, mold release agents and the like.

[Manufacturing method of resin composition]
The resin composition of the present embodiment can be produced by melt-kneading the above-mentioned components (a) to (d), and if necessary, the components (e), (f), and other components.

The melt-kneading machine that performs melt-kneading is not limited to the following, but for example, heat-melt-kneading by a single-screw extruder, a multi-screw extruder including a twin-screw extruder, a roll, a kneader, a Brabender plastograph, a Banbury mixer, or the like. A machine is mentioned, but a twin-screw extruder is particularly preferable from the viewpoint of kneading property. Specific examples thereof include the ZSK series manufactured by COPERION, the TEM series manufactured by Toshiba Machine Co., Ltd., and the TEX series manufactured by Japan Steel Works, Ltd.

A preferred manufacturing 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 or more and 60 or less, and more preferably 30 or more and 50 or less.

The configuration of the extruder is not particularly limited, but for example, a first raw material supply port is provided on the upstream side, a first vacuum vent is provided downstream of the first raw material supply port, and a second raw material supply port is provided downstream of the first raw material supply port in the flow direction of the raw material ( If necessary, a third and fourth raw material supply port may be further provided), and a second vacuum vent is further provided downstream thereof. In particular, a kneading section is provided upstream of the first vacuum vent, a kneading section is provided between the first vacuum vent and the second raw material supply port, and between the second to fourth raw material supply ports and the second vacuum vent. It is more preferable to provide a kneading section on the surface.

The method of supplying the raw material to the second to fourth raw material supply ports is not particularly limited, but the extruder side is opened rather than the simple addition supply from the opening of the extruder second to fourth raw material supply ports. The method of supplying from the mouth using a forced side feeder tends to be more stable and is preferable.

In particular, when powder is contained in the raw material and it is desired to reduce the generation of crosslinked products and carbides due to the thermal history of the resin, a method using a forced side feeder supplied from the extruder side is more preferable, and the forced side feeder is used as the second. A method of providing the powders of these raw materials at the fourth raw material supply port and supplying them in a divided manner is more preferable.

When adding a liquid raw material, it is preferable to add it into the extruder using a plunger pump, a gear pump or the like.

The upper opening of the extruder 2nd to 4th raw material supply ports can also be used as an opening for removing the air carried together.

The melt-kneading temperature and screw rotation speed in the melt-kneading step of the resin composition are not particularly limited, but are usually equal to or higher than the melting point temperature of the crystalline resin in the crystalline resin and the temperature of the non-crystalline resin. It is possible to select a temperature at which heating and melting can be carried out reasonably at a temperature equal to or higher than the glass transition temperature. Usually, the temperature is arbitrarily selected from 200 to 370 ° C., and the screw rotation speed is 100 to 1200 rpm.

As one of the specific manufacturing methods of the resin composition of the present invention by a preferable twin-screw extruder, for example, a polyphenylene ether-based resin as a component (a), titanium oxide as a component (c), and calcium carbonate as a component (d). The elastomer of the component (f) is supplied to the first supply port of the twin-screw extruder, the heating and melting zone is set to the melting temperature of the polyphenylene ether-based resin, and the screw rotation speed is 100 to 1200 rpm, preferably 200 to 500 rpm. In a state where the components (a), (c), (d) and (f) are melt-kneaded, the condensed phosphoric acid ester of the component (e) is melt-kneaded from the second supply port of the twin-screw extruder. Examples thereof include a method in which the inorganic filler of the component (b) is supplied from the flame retardant and the third supply port, and further melt-kneaded. Further, the positions for supplying the components (a), (c), (d) and (f) to the twin-screw extruder are collectively supplied from the first supply port of the extruder as described above. Alternatively, a second supply port, a third supply port, and a fourth supply port may be provided and each component may be divided and supplied.

Further, in order to reduce the generation of crosslinked products and carbides due to the thermal history of the resin in the presence of oxygen, the oxygen concentration of each process line in the addition path of each raw material to the extruder is kept below 1.0% by volume. Is preferable. The addition route is not particularly limited, and specific examples thereof include a pipe, a heavy-duty feeder having a refill tank, a pipe, a supply hopper, and a twin-screw extruder in order from the stock tank. The method for maintaining the low oxygen concentration as described above is not particularly limited, but a method of introducing the inert gas into each process line having improved airtightness is effective. Usually, it is preferable to introduce nitrogen gas to maintain the oxygen concentration below 1.0% by volume.

The method for producing the resin composition described above is the resin composition of the present embodiment when the polyphenylene ether-based resin of the component (a) and the elastomer of the component (f) contain a powder-like component (volume average particle size is less than 10 μm). When a product is manufactured using a twin-screw extruder, it has the effect of further reducing the residue in the screw of the twin-screw extruder, and further, in the resin composition obtained by the above-mentioned manufacturing method, black spot foreign matter and carbides It has the effect of reducing the occurrence of such factors.

As a specific method for producing the resin composition of the present embodiment, an extruder in which the oxygen concentration of each raw material supply port is controlled to less than 1.0% by volume is used, and any of the following methods 1 to 3 is carried out. It is preferable to do so.
1. 1. All or part of the component (a), the component (c), the component (d) and the component (f) contained in the resin composition of the present embodiment, and if necessary, a part of the component (b) are melt-kneaded. (1st kneading step), the remaining amount of (a) component, (c) component, (d) component and (f) component, (e) with respect to the kneaded product in the molten state obtained in the first kneading step. The entire amount of the components is supplied and melt-kneaded (second kneading step), and the kneaded product in the molten state obtained in the second kneading step is melt-kneaded by supplying all or part of (b) the components (b). Third kneading process), manufacturing method.
2. 2. The components (a), (e), and (f) contained in the resin composition of the present embodiment are melt-kneaded (first kneading step), cooled once, pelletized, and then the other (b). A production method in which the entire amount of the component, the component (c) and the component (d) is supplied and melt-kneaded (second kneading step).
3. 3. A method of melt-kneading all the components (a) to (f) contained in the resin composition of the present embodiment.

In particular, the polyphenylene ether which is the raw material of the component (a) and the hydrogenated block copolymer of the component (f) depending on the molecular structure may be in the form of powder, and the component (e) may be in the liquid state. Poor biteability makes it difficult to increase production per hour. Further, since the residence time in the resin extruder becomes long, thermal deterioration is likely to occur. From the above, the resin composition obtained by the above-mentioned production method 1 or 2 is superior in the mixing property of each component as compared with the resin composition obtained by the production method 3 and generates crosslinked products and carbides due to thermal deterioration. This is more preferable because a resin composition having excellent productivity and quality can be obtained by reducing the amount of resin and increasing the amount of resin produced per hour.

Here, in the first kneading step to the second kneading step, it is possible to avoid putting the kneaded product in a molten state, melting the component (a) once, pelletizing it, and then melting it again.

〔Molding〕
The molded product of the resin composition of the present embodiment includes optical equipment mechanism parts, light source lamp peripheral parts, metal film laminated substrate sheet or film, hard disk internal parts, optical fiber connector ferrules, printer parts, copier parts, automobile radiator tanks. It can be widely used as a molded product such as a part in an automobile engine room such as a part or an automobile lamp part.

Hereinafter, the present embodiment will be described with reference to specific examples and comparative examples, but the present embodiment is not limited thereto.
In addition, Examples 7 and 9 are described as reference examples.

The method for measuring the physical properties used in Examples and Comparative Examples is shown below.

((1) Charpy impact test)
Charpy impact strength (kJ / m ² ) was measured by the method described in ISO 179. It was evaluated that the higher the value, the better the impact resistance.

((2) Vibration fatigue test)
Using a hydraulic servo fatigue tester (EHF-50-10-3, manufactured by Saginomiya Seisakusho Co., Ltd.) according to JIS K7118 and K7119, a tensile load (50 MPa) is applied with a sine wave at a frequency of 30 Hz in an atmosphere of 23 ° C. Then, the number of vibrations that broke was calculated. It was evaluated that the larger the number of vibrations until breakage, the better the vibration-resistant fatigue characteristics.

((3) Whiteness)
The L value was determined using a colorimetric color difference meter (ZE-2000 manufactured by Nippon Denshoku Industries Co., Ltd.) according to JIS Z8715. It was evaluated that the higher the L value, the higher the whiteness.

((4) Flame retardant)
The test was carried out according to the vertical combustion test method of UL94 (standard defined by Under Writer's Laboratories Inc. in the United States).

The raw materials used in Examples and Comparative Examples are shown below.

<(A) Polyphenylene ether-based resin>
(A1): PPE (polyphenylene ether)
Polyphenylene ether obtained by oxidative polymerization of 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) Average diameter 13 μm, average length 3,000 μm. Glass fiber surface-treated with an aminosilane-based coupling agent.
(B2) Average diameter 6 μm, average length 3,000 μm. Carbon fiber surface-treated with an epoxy silane coupling agent.
(B3) The average plate diameter is 130 μm and the average thickness is 5 μm. Glass flakes surface-treated with an aminosilane coupling agent.
(B4) Talc with an average particle size of 3 μm (trade name “Hytron A”, manufactured by Takehara Chemical Industry Co., Ltd.).
(B5) Carbon black (trade name "# 980", manufactured by Mitsubishi Chemical Corporation).

<(C) Titanium oxide>
(C1) Titanium oxide (primary particle size 0.3 μm, trade name “RTC-30”, manufactured by HUNTSMAN (UK)).

<(D) Calcium carbonate>
(D1) Calcium carbonate having an average particle size of 12 μm.
(D2) Calcium carbonate having an average particle size of 6 μm (trade name “Sunlight SL-100”, manufactured by Takehara Chemical Industry Co., Ltd.).
(D3) Calcium carbonate having an average particle size of 1.3 μm (trade name “Sunlight SL-2200”, manufactured by Takehara Chemical Industry Co., Ltd.).
(D4) Calcium carbonate having an average particle size of 0.08 μm (trade name “Neorite SP”, manufactured by Takehara Chemical Industry Co., Ltd.).

<(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) Polystyrene-Water having a hydrogenated polybutadiene-polystyrene structure, having a bonded styrene content of 33%, a number average molecular weight of 246,000, a molecular weight distribution of 1.07, and a hydrogenation rate of 99.8% in the polybutadiene part. A hydrogenated block copolymer was synthesized.
(F2) A block copolymer having a polystyrene-polybutadiene-polystyrene structure, having 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 to 13], [Comparative Examples 1 to 6]
A resin composition was produced using a twin-screw extruder ZSK-40 (manufactured by WERNER & PFLEDERER). In this twin-screw extruder, a first raw material supply port is provided on the upstream side with respect to the flow direction of the raw material, a first vacuum vent, a second raw material supply port, and a third raw material supply port are provided downstream of the first raw material supply port. A second vacuum vent was provided downstream. The second raw material supply port was made by using a gear pump from the upper opening of the extruder.
Using the extruder set as described above, the components (a), (c), (d), and (f) have the composition shown above from the first raw material supply port, and (e) condensed phosphoric acid. Ester-based flame retardant is added from the second raw material supply port, and (b) the inorganic filler is added from the third raw material supply port, and melted under the conditions of extrusion temperature 240 to 310 ° C., screw rotation speed 300 rpm, and discharge rate 100 kg / hour. It was kneaded to produce pellets. Of the components (b), the components (b4) and (b5) were added from the first raw material supply port.
The pellets of this resin composition were supplied to a screw in-line type injection molding machine set at 250 to 310 ° C. to obtain a molded product for ASTM TYPE1 vibration fatigue measurement under injection molding conditions at a mold temperature of 60 to 120 ° C. The molded product obtained here was left at 23 ° C. and 50% relative humidity for 24 hours or more, and (2) vibration fatigue test and (3) whiteness measurement were performed.
Further, the test piece type A was molded according to ISO 10724-1 under the same injection molding conditions. (1) Charpy impact strength (ISO 179) was measured using this test piece.
Further, 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. Using this, a vertical combustion test based on UL94 was conducted, and (4) flame retardancy was evaluated.
These results are also shown in Tables 1 and 2.
As shown in Tables 1 and 2, it was found that the resin compositions of Examples 1 to 13 were excellent in impact resistance and vibration fatigue characteristics, and were also excellent in whiteness.
Comparative Examples 1 to 6 were inferior in impact resistance, vibration fatigue characteristics, and whiteness at least one of them as compared with Examples.

The molded product molded from the resin composition of the present embodiment has excellent white coloring property, and is excellent in impact resistance and vibration fatigue characteristics, so that the degree of freedom in designing the resin molded product can be increased. Therefore, it can be used as various parts in electrical / electronic equipment, automobile equipment, chemical equipment, and optical equipment. For example, chassis and cabinets such as digital versatile discs, optical equipment mechanical parts such as optical pickup slide bases, and parts around light source lamps. Metal film Laminated substrate sheet or film, hard disk internal parts, optical fiber connector ferrule, laser beam printer internal parts (toner cartridge, etc.), inkjet printer internal parts, copier internal parts, automobile radiator tank parts, etc. , Has industrial potential as an automobile lamp part, etc.

Claims (8)

For a total of 100 parts by mass of (a) polyphenylene ether-based resin and (b) inorganic filler
(A) 40 to 99 parts by mass of polyphenylene ether resin,
(B) 1 to 60 parts by mass of the inorganic filler,
(C) Titanium oxide in an amount of 0.1 to 5 parts by mass,
(D) Contains 0.3 to 10 parts by mass of calcium carbonate
The inorganic filler (b) is made of glass fiber, carbon fiber, silicone fiber, silica / alumina fiber, silicon nitride fiber, silicon carbide fiber, potassium titanate whisker , silicon nitride whisker, wallastnite fiber , or aluminum . fibers, fibers of titanium, copper fibers, glass flakes, mica, and at least one der selected from the group consisting of aluminum flakes is,
The average particle diameter of the (d) calcium carbonate Ru 0.5~6μm der,
A resin composition characterized by the above. The inorganic filler (b) is made of glass fiber, carbon fiber, silicone fiber, silica / alumina fiber, silicon nitride fiber, silicon carbide fiber, potassium titanate whisker , silicon nitride whisker, wallastnite fiber , or aluminum . It is at least one selected from the group consisting of fibers , titanium fibers , and copper fibers , and is represented by (b) the ratio of the average diameter (D) to the average length (L) of the inorganic filler. The resin composition according to claim 1, wherein the amount is 5 or more and 500 or less. The (b) inorganic filler is at least one selected from the group consisting of flake-shaped glass, mica, and aluminum flakes, and has the average thickness (H) and average plate diameter (R) of the (b) inorganic filler. The resin composition according to claim 1, wherein the R / H represented by the ratio is 5 or more and 3000 or less. (A) The polyphenylene ether-based resin contains polyphenylene ether and a polystyrene-based resin.
The resin composition according to any one of claims 1 to 3 , wherein the mass ratio of the polyphenylene ether to the polystyrene-based resin (polyphenylene ether / polystyrene-based resin) is 99/1 to 5/95. The resin composition according to claim 4, wherein the polystyrene-based resin is atactic polystyrene and / or high-impact polystyrene. Any one of claims 1 to 5 , which contains 2 to 20 parts by mass of (e) a condensed phosphoric acid ester flame retardant with respect to a total of 100 parts by mass of (a) a polyphenylene ether-based resin and (b) an inorganic filler. The resin composition according to. The resin composition according to any one of claims 1 to 6 , which contains 1 to 20 parts by mass of (f) an elastomer with respect to a total of 100 parts by mass of (a) a polyphenylene ether-based resin and (b) an inorganic filler. .. (F) The resin composition according to claim 7, wherein the elastomer is a block copolymer and / or a hydrogenated block copolymer.