JP5550393B2 - Resin composition - Google Patents

Description

  The present invention relates to a resin composition that can be used in the electric / electronic field, the automobile field, and other various industrial material fields.

  Polypropylene resins are low specific gravity and inexpensive plastics, and are excellent in chemical resistance, solvent resistance, moldability, etc., so they are used in various fields such as automotive parts, electrical / electronic equipment parts, and household electrical appliances. ing. On the other hand, polyphenylene ether-based resin is known as an engineering plastic excellent in flame retardancy, heat resistance, dimensional stability, non-water absorption and electrical properties, but has poor melt flowability and inferior molding processability, and There is a disadvantage that it is inferior in solvent resistance and impact resistance. Various compositions have been proposed for the purpose of making up for the disadvantages of these polypropylene resins and polyphenylene ether resins, and Patent Documents 1 to 3 improve mechanical strength and linear expansion coefficient. The technology is described.

JP-A-63-113047 JP-A-63-125543 JP 2004-285089 A

However, although these prior documents describe a technique for reducing the linear expansion coefficient, improvement of anisotropy of the obtained resin composition is not sufficient. In general, it is known that inorganic fillers are effective in reducing the linear expansion coefficient. However, in reality, there is no known means for reducing the anisotropy while reducing the linear expansion coefficient.
This invention is made | formed in view of the said situation, and makes it a subject to provide the resin composition excellent in the balance of rigidity, thermal-rigidity retention, a linear expansion coefficient, and anisotropy.

  In order to impart a balance of high level of rigidity, linear expansion coefficient, and anisotropy to a resin composition containing a polypropylene resin, a polyphenylene ether resin, and a hydrogenated block copolymer as an admixture. As a result of intensive studies, the amount of each component was adjusted to a specific range, and further by melt-kneading using a specific inorganic filler, rigidity, thermal rigidity retention, which could not be achieved by conventional techniques, The present inventors have found that a resin composition having an excellent balance of linear expansion coefficient and anisotropy can be obtained, and have completed the present invention.

That is, the present invention is as follows.
[1]
(A) 20 to 99 parts by mass of a polypropylene resin,
(B) 80-1 parts by mass of a polyphenylene ether resin,
(C) vinyl aromatic compound-conjugated diene compound block co-polymer weight of (c) bonded vinyl aromatic compound is 15% by mass or more and 45% by mass or less with respect to 100 parts by mass in total of component (a) and component (b). 1-30 parts by mass of combined hydrogenated product,
A vinyl aromatic compound-conjugated diene compound block in which the amount of (d) bonded vinyl aromatic compound exceeds 45% by mass and is 95% by mass or less with respect to 100 parts by mass in total of the component (a) and the component (b). 0-30 parts by weight of hydrogenated copolymer
(E) fibrous filler,
(F) at least one inorganic filler selected from the group consisting of kaolin clay, talc, and calcium carbonate, having an average particle size of 1 μm or less,
The resin composition whose sum total of the said (e) component and the said (f) component is 40-140 mass parts with respect to 100 mass parts in total of the said (a) component and the said (b) component.
[2]
The resin composition according to the above [1], wherein the polypropylene resin as the component (a) has a melt flow rate (MFR) (230 ° C., load 2.16 Kg) of 0.1 to 150 g / 10 min.
[3]
The component (c) is a hydrogenated styrene-butadiene block copolymer, and the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds in the butadiene polymer block is 65 to 90%. A resin composition according to the above [1] or [2].
[4]
The resin composition according to any one of [1] to [3], wherein the component (d) is a hydrogenated product of a styrene-butadiene block copolymer.
[5]
Resin composition in any one of said [1]-[4] whose mass ratio of said (e) component / said (f) component is 80 / 20-20 / 80.
[6]
The resin composition according to any one of [1] to [5], wherein the component (e) is at least one selected from the group consisting of glass fiber, carbon fiber, metal fiber, inorganic fiber, and wollastonite. .
[7]
The component (e) is a wollastonite having an average fiber diameter D of 1 to 30 μm, an average fiber length L of 10 to 500 μm, and an aspect ratio (L / D) of 4 to 30, according to the above [1] to [6]. Any resin composition.
[8]
The resin composition according to any one of [1] to [7], wherein the component (f) is kaolin clay.
[9]
The resin composition according to any one of [1] to [8], wherein the component (a) forms a matrix phase and the component (b) forms a dispersed phase.
[10]
A molded article comprising the resin composition according to any one of [1] to [9].
[11]
The molded article according to the above [10], which is an automotive exterior part.

  According to the present invention, it is possible to provide a resin composition having an excellent balance of rigidity, thermal rigidity retention, linear expansion coefficient, and anisotropy.

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

The resin composition of the present embodiment is
(A) 20 to 99 parts by mass of a polypropylene resin,
(B) 80-1 parts by mass of a polyphenylene ether resin,
(C) vinyl aromatic compound-conjugated diene compound block co-polymer weight of (c) bonded vinyl aromatic compound is 15% by mass or more and 45% by mass or less with respect to 100 parts by mass in total of component (a) and component (b). 1-30 parts by mass of combined hydrogenated product,
A vinyl aromatic compound-conjugated diene compound block in which the amount of (d) bonded vinyl aromatic compound exceeds 45% by mass and is 95% by mass or less with respect to 100 parts by mass in total of the component (a) and the component (b). 0-30 parts by weight of hydrogenated copolymer
(E) fibrous filler,
(F) at least one inorganic filler selected from the group consisting of kaolin clay, talc, and calcium carbonate, having an average particle size of 1 μm or less,
The total of the (e) component and the (f) component is 40 to 140 parts by mass with respect to 100 parts by mass of the total of the (a) component and the (b) component.

[(A) component]
The polypropylene resin that is the component (a) of the present embodiment is not particularly limited. For example, the crystalline propylene homopolymer; the crystalline propylene homopolymer portion obtained in the first step of polymerization, and the second of polymerization Crystalline propylene having a propylene-ethylene random copolymer portion obtained by copolymerizing propylene, ethylene and / or at least one other α-olefin (for example, butene-1, hexene-1, etc.) after the step -An ethylene block copolymer etc. are mentioned. A mixture of a crystalline propylene homopolymer and a crystalline propylene-ethylene block copolymer may also be used. These polypropylene resins may be used alone or in combination of two or more.

  The method for producing such a polypropylene resin is not particularly limited. For example, in the presence of a titanium trichloride catalyst or a titanium halide catalyst supported on a carrier such as magnesium chloride and an alkylaluminum compound, a polymerization temperature range of 0 to 100 ° C. The polymerization pressure can be obtained by polymerization in the range of 3 to 100 atm. At this time, a chain transfer agent such as hydrogen may be added to adjust the molecular weight of the polymer. The polymerization method is not particularly limited, and either a batch method or a continuous method may be used.

  Further, solution polymerization in a solvent such as butane, pentane, hexane, heptane, octane, etc .; slurry polymerization; bulk polymerization in a monomer without solvent; gas phase polymerization method in a gaseous monomer, etc. can also be applied.

  Furthermore, in order to increase the isotacticity and polymerization activity of the obtained polypropylene resin, an electron donating compound can be used as an internal donor component or an external donor component as a third component in addition to the polymerization catalyst. The type of the electron donating compound is not particularly limited, and known compounds can be used. For example, ester compounds such as ε-caprolactone, methyl methacrylate, ethyl benzoate and methyl toluate; phosphorous acid esters such as triphenyl phosphite and tributyl phosphite; phosphoric acid derivatives such as hexamethylphosphoramide; Examples include alkoxy ester compounds, aromatic monocarboxylic acid esters, aromatic alkyl alkoxy silanes, aliphatic hydrocarbon alkoxy silanes, various ether compounds, various alcohols, and / or various phenols.

  The (a) polypropylene resin in the present embodiment can be obtained by the above-described method or the like. Moreover, even if it is a polypropylene-type resin which has what kind of crystallinity and melting | fusing point, you may use independently and may use 2 or more types together.

  The melt flow rate (MFR) (230 ° C., load 2.16 kg) of the polypropylene resin is preferably 0.01 to 150 g / 10 minutes, more preferably 0.1 to 100 g / 10 minutes. By setting the MFR within the above range, the fluidity and rigidity balance tends to be improved.

  Further, in addition to the above polypropylene resin, a polypropylene resin and an α, β-unsaturated carboxylic acid or a derivative thereof in a molten state or in a solution state in the presence or absence of a radical generator 30 to 30 You may use the modified polypropylene resin obtained by making it react at 350 degreeC. Examples of the modified polypropylene resin include polypropylene resins obtained by grafting or adding 0.01 to 10% by mass of α, β-unsaturated carboxylic acid or a derivative thereof. The mixing ratio of the polypropylene resin and the modified polypropylene resin is not particularly limited and can be arbitrarily determined.

[Component (b)]
The polyphenylene ether resin (hereinafter sometimes simply referred to as “PPE”), which is the component (b) of the present embodiment, is a homopolymer having a repeating unit structure represented by the following formula (1) and / or It is a copolymer. The reduced viscosity (0.5 g / dL chloroform solution, measured at 30 ° C.) is not particularly limited, but is preferably in the range of 0.15 to 2.50, more preferably 0.30 to 2.00, More preferably, it is the range of 0.35-2.00.

In the formula, R ₁ , R ₂ , R ₃ , and R ₄ each independently represent a hydrogen atom, a halogen atom, a primary or secondary alkyl group having 1 to 7 carbon atoms, a phenyl group, or a haloalkyl group. , An aminoalkyl group, a hydrocarbonoxy group or a halohydrocarbonoxy group in which at least two carbon atoms separate a halogen atom and an oxygen atom.

  The polyphenylene ether-based resin in the present embodiment is not particularly limited, and a known one can be used. 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) Phenylene ether), poly (2,6-dichloro-1,4-phenylene ether) and the like, and 2,6-dimethylphenol and other phenols (for example, 2,3,6-trimethylphenol and 2 A polyphenylene ether copolymer such as (methyl-6-butylphenol) can also be used.

  Among these, poly (2,6-dimethyl-1,4-phenylene ether), a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol is preferable, and poly (2,6-dimethylphenol) is preferable. -1,4-phenylene ether) is more preferable.

  The production method of the polyphenylene ether resin is not particularly limited, and a conventionally known method can be used. For example, it can be easily produced by, for example, oxidative polymerization of 2,6-xylenol using a complex of cuprous salt and amine described in US Pat. No. 3,306,874 as a catalyst. Alternatively, U.S. Pat. No. 3,306,875, U.S. Pat. No. 3,257,357, U.S. Pat. No. 3,257,358, JP-B-52-17880, JP-A-50-51197, JP-A-63-152628. It can be manufactured by a method described in a gazette or the like.

  Further, in addition to the polyphenylene ether-based resin, the polyphenylene ether-based resin and the styrene monomer or derivative thereof may be 80 to 350 in a molten state, a solution state, or a slurry state in the presence or absence of a radical generator. You may use together the modification | denaturation polyphenylene ether-type resin obtained by making it react at ° C. Examples of such modified polyphenylene ether resins include polyphenylene ether resins obtained by grafting or adding 0.01 to 10% by mass of a styrene monomer or a derivative thereof. The mixing ratio of the polyphenylene ether resin and the modified polyphenylene ether resin is not limited, and can be mixed at an arbitrary ratio.

  Moreover, as polyphenylene ether resin, what mixed polystyrene, syndiotactic polystyrene, and / or high impact polystyrene in polyphenylene ether resin can be used suitably other than the resin mentioned above.

  More preferably, 100 parts by mass of the polyphenylene ether resin is a mixture of polystyrene, syndiotactic polystyrene, high impact polystyrene and a mixture thereof in a range not exceeding 400 parts by mass in total.

[Component (c)]
The component (c) in the present embodiment is a hydrogenated product of (c) vinyl aromatic compound-conjugated diene compound block copolymer having a bound vinyl aromatic compound content of 15% by mass or more and 45% by mass or less.
(C) The hydrogenated block copolymer comprises at least part of a block copolymer containing a polymer block A mainly composed of a vinyl aromatic compound and a polymer block B mainly composed of a conjugated diene compound. It is a copolymer that is added and the amount of the bound vinyl aromatic compound is adjusted in the range of 15% by mass or more and 45% by mass or less.

  The component (c) acts as at least one of an admixture or an impact resistance imparting agent for the polypropylene resin as the component (a) and the polyphenylene ether resin as the component (b). The component (c) preferably exhibits an effect as an admixture in the resin composition (an effect of finely emulsifying and dispersing the polyphenylene ether resin in the polypropylene resin). In this case, in the resin composition, the component (a) forms a matrix phase, and the component (b) forms a dispersed phase. When the resin composition has the above structure, the moldability tends to be improved.

(Polymer block A mainly composed of vinyl aromatic compounds)
The polymer block A mainly composed of a vinyl aromatic compound is a homopolymer block of a vinyl aromatic compound or a copolymer block of a vinyl aromatic compound and a conjugated diene compound.

  In the polymer block A, “mainly composed of a vinyl aromatic compound” means that the polymer block A contains a vinyl aromatic compound in an amount of more than 50% by mass, and the vinyl aromatic compound is 70% by mass or more. It is preferable to contain.

  Examples of the vinyl aromatic compound constituting the polymer block A include styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, diphenylethylene, and the like. These may be used individually by 1 type and may use 2 or more types. Among the above, styrene is preferable.

  The block copolymer before hydrogenation of the component (c) has a bonded vinyl aromatic compound content (also referred to as “bound vinyl aromatic compound amount”) of 15 mass% or more and 45 mass% or less, Preferably they are 20 mass% or more and 45 mass% or less. In addition, the measurement of the amount of bonded vinyl aromatic compounds can be performed by NMR.

  The number average molecular weight of the polymer block A is not particularly limited, but is preferably 15000 or more. When the number average molecular weight is 15000 or more, the miscibility of the resin composition tends to be more excellent. The number average molecular weight of the polymer block A can be measured by GPC (moving layer: tetrahydrofuran, standard material: polystyrene).

(Polymer block B mainly composed of conjugated diene compound)
The polymer block B mainly composed of a conjugated diene compound is a homopolymer block of a conjugated diene compound or a random copolymer block of a conjugated diene compound and a vinyl aromatic compound.

  In the polymer block B, “consisting mainly of a conjugated diene compound” means that the polymer block B contains more than 50% by mass of the conjugated diene compound, and 70% by mass or more of the conjugated diene compound. Is preferred.

  Examples of the conjugated diene compound constituting the polymer block B include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like. These may be used individually by 1 type and may use 2 or more types together. Among the above, butadiene, isoprene and combinations thereof are preferable.

  Regarding the microstructure of the polymer block B (bonded form of the conjugated diene compound), the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds (hereinafter also referred to as “total vinyl bond amount”). Preferably it is 45 to 90%, more preferably 50 to 90%. By setting the total vinyl bond amount within the above range, excellent miscibility tends to be obtained. By making the total vinyl bond amount 45% or more, the dispersibility of the polyphenylene ether resin dispersed in the resin composition tends to be good, and by making the total vinyl bond amount 90% or less, it is economical. It tends to be excellent. In particular, when the polymer block B is a polymer mainly composed of butadiene, the total vinyl bond content of the polymer block B is preferably 65 to 90%.

  In this Embodiment, the total vinyl bond amount of the polymer block B can be measured with an infrared spectrophotometer. In addition, the calculation method of total vinyl bond amount is Analytical Chemistry, Volume 21, No. 8, according to the method described in August 1949.

The component (c) is a hydrogenated block copolymer obtained by hydrogenating a block copolymer containing at least the polymer block A and at least the polymer block B.
When the block polymer A is “A” and the block polymer B is “B”, as the component (c), for example, AB, ABA, BABA, (A -B-) A hydrogenated product of vinyl aromatic compound-conjugated diene compound block copolymer having a structure such as 4Si, ABABA, or the like. (A-B-) 4Si is a reaction residue of a polyfunctional coupling agent such as silicon tetrachloride or tin tetrachloride, or a residue of an initiator such as a polyfunctional organolithium compound.

  The molecular structure of the block copolymer including the block polymer A and the block polymer B is not particularly limited, and may be, for example, linear, branched, radial, or any combination thereof. In the polymer block A and the polymer block B, the distribution of vinyl aromatic compound or conjugated diene compound in the molecular chain in each polymer block is random and tapered (in which the monomer component increases or decreases along the molecular chain). , May be partly block-shaped or any combination thereof. Further, when there are two or more polymer blocks A or polymer blocks B in the repeating unit, each polymer block may have the same structure or a different structure.

  The number average molecular weight of the block copolymer before hydrogenation of (c) component becomes like this. Preferably it is 5000-1 million, More preferably, it is 1000-800000, More preferably, it is 30000-500000. If the number average molecular weight is too large, mobility may be reduced, and emulsification and dispersion of component (b) may be difficult. The number average molecular weight can be measured by gel permeation chromatography (GPC, solvent: tetrahydrofuran, standard material: polystyrene).

  (C) It is preferable that the molecular weight distribution of the block copolymer before hydrogenation is 10 or less. The molecular weight distribution can be calculated by the ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) measured by gel permeation chromatography (GPC, solvent: tetrahydrofuran, standard substance: polystyrene).

  Although it does not specifically limit as a hydrogenation rate with respect to the conjugated diene compound in (c) component, It is preferable that it is 50% or more of the double bond originating in a conjugated diene compound, More preferably, it is 80% or more, More preferably 90% or more. In the present embodiment, the hydrogenation rate can be measured by NMR.

  (C) It does not specifically limit as a manufacturing method of the hydrogenated block copolymer of a component, For example, a well-known manufacturing method is employable. For example, Japanese Patent Application Laid-Open Nos. 47-11486, 49-66743, 50-75651, 54-126255, and 56-10542 are disclosed. No. 5, JP-A 56-62847, JP-A 56-100900, JP-A 2-300218, British Patent 1130770, US Pat. No. 3,281,383, US Pat. No. 3639517 The methods described in the specification, British Patent No. 1020720, US Pat. No. 3,333,024 and US Pat. No. 4,501,857 can be used.

  Further, the hydrogenated block copolymer of component (c) is a hydrogenated block copolymer and an α, β-unsaturated carboxylic acid or derivative thereof (ester compound or acid anhydride compound) in the presence of a radical generator. The modified hydrogenated block copolymer obtained by making it react at 80-350 degreeC in a molten state, a solution state, or a slurry state in the bottom or absence. In this case, it is preferable that the α, β-unsaturated carboxylic acid or derivative thereof is grafted or added to the hydrogenated block copolymer at a ratio of 0.01 to 10% by mass. Further, it may be a mixture of the above hydrogenated block copolymer and the modified hydrogenated block copolymer in an arbitrary ratio.

The component (d) in the present embodiment is a hydrogenated product of a vinyl aromatic compound-conjugated diene compound block copolymer having a bonded vinyl aromatic compound amount of more than 45% by mass and 95% by mass or less.
The hydrogenated block copolymer (d) used in the present embodiment is a block copolymer comprising a polymer block A mainly composed of a vinyl aromatic compound and a polymer block B mainly composed of a conjugated diene compound. It is a copolymer that is at least partially hydrogenated, and the amount of the bound vinyl aromatic compound is adjusted to a range of more than 45% by mass and 95% by mass or less. Component (d) is the same vinyl aromatic compound-conjugated diene as component (c) except that the amount of bound vinyl aromatic compound is adjusted to a range of more than 45% by mass and 95% by mass or less. A compound block copolymer can be used.

[(E) component]
The component (e) in the present embodiment is a fibrous filler. Examples of the fibrous filler as the component (e) include inorganic fillers such as glass fiber, carbon fiber, metal fiber, wollastonite, silicon carbide whisker, silicon nitride whisker, fibrous aluminum oxide, and acicular titanium oxide. Among the above, wollastonite, silicon carbide whisker, and silicon nitride whisker are preferable, and wollastonite is more preferable. The said inorganic filler is used individually by 1 type or in combination of 2 or more types. The average fiber length L, average fiber diameter D, and aspect ratio (L / D) of the fibrous filler are not particularly limited as long as the effects of the present invention are not impaired, but in the case of wollastonite, the average fiber Those having a diameter D of 1 to 30 μm, an average fiber length L of 10 to 500 μm, and an aspect ratio (L / D) of 4 to 30 are preferably used.

Here, the average fiber length L and the average fiber diameter D of the fibrous filler can be determined as follows.
The fibrous filler is dispersed in water, transferred onto a glass slide, and observed under an optical microscope. Using an image analysis device, the length of 400 arbitrarily selected fibrous fillers is measured and determined by the following equation.
Average fiber diameter D = ΣLi / n (number average)
Average fiber length L = ΣLi ² / ΣLi (weight average)
Here, in the formula, Li indicates the length of each fibrous filler (L1, L2,..., L400), and Li ² indicates the length of each corresponding fibrous filler. Square (L1 ² , L2 ² ,..., L400 ² ), n represents the number of observed fibrous fillers.

  The aspect ratio of the wollastonite is 4-30, more preferably 4-20. When the aspect ratio is less than 4, the effect of improving the linear expansion coefficient tends to be insufficient, and when it exceeds 30, the appearance of the molded product tends to deteriorate.

  Furthermore, the wollastonite in the present embodiment may be surface-treated with a conventionally known surface treating agent. Examples of the surface treatment agent include silane coupling agents and titanate coupling agents containing amino groups and epoxy groups. Such a surface treating agent can be pretreated on the surface of wollastonite, or may be added when wollastonite is mixed.

[Component (f)]
Component (f) in the present embodiment is at least one inorganic filler selected from the group consisting of kaolin clay, talc, and calcium carbonate having an average particle size of 1 μm or less.
By setting the average particle size of the inorganic filler to 1 μm or less, the balance between the linear expansion coefficient and the anisotropy is improved due to a synergistic effect with the component (e). Moreover, among kaolin clay, talc, and calcium carbonate, kaolin clay is preferably used, and Minamata kaolin clay is more preferably used. Minamata kaolin clay is a method obtained by dispersing raw kaolin clay in water when separating and purifying kaolin clay having a desired average primary particle size, that is, obtained by using the Minamata method. . By purifying and bleaching using water, impurities are removed and whiteness is increased. Moreover, since the particle size is adjusted by a water tank, it has a sharp particle size distribution. Here, the average particle diameter of the inorganic filler as the component (f) can be measured by a centrifugal sedimentation light transmission method.

  The component (f) may be surface-treated with a conventionally known surface treating agent from the viewpoint of improving mechanical strength. The type of the surface treatment agent is not particularly limited. For example, vinyl silane compounds such as vinyltrichlorosilane, vinyltriethoxysilane and γ-methacryloxypropyltrimethoxysilane; epoxy silanes such as γ-glycidoxypropyltrimethoxysilane Compounds; sulfur-based silane compounds such as bis- (3-triethoxysilylpropyl) tetrasulfide and γ-mercaptopropyltrimethoxysilane; γ-aminopropyltriethoxysilane and N-phenyl-γ-aminopropyltrimethoxysilane Examples include aminosilane compounds such as mercaptosilane compounds. The said silane compound may be used individually by 1 type, and may be used in combination of 2 or more type. Among the above, from the viewpoint of easy handling as a powder raw material and sufficient ability to exhibit flame retardancy, sulfur-based silane compounds are preferable, and mercaptosilane compounds are more preferable.

The resin composition of the present embodiment is composed of the above components (a) to (f) as basic components.
In the resin composition of the present embodiment, the amount of component (a) is 20 to 99 parts by mass, preferably 25 to 95 parts by mass. When the blending amount of component (a) is less than 20 parts by mass, the resulting resin composition has an excellent coefficient of linear expansion, but is unfavorable because of poor heat resistance. On the other hand, if it exceeds 99 parts by mass, the moldability and fluidity are good, but the linear expansion is inferior.

  (B) The compounding quantity of a component is 80-1 mass part, Preferably it is 75-5 mass part. When the blending amount of component (b) exceeds 80 parts by mass, the resulting resin composition is excellent in heat resistance and linear expansion coefficient, but is unfavorable because of poor molding processability and solvent resistance. Moreover, since it is inferior to heat resistance as it is less than 1 mass part, it is unpreferable.

  Next, the compounding quantity of (c) component is 1-30 mass parts with respect to a total of 100 mass parts of (a) component and (b) component, Preferably it is 1-20 mass parts. When the amount of the component (c) is less than 1 part by mass, the effect as an admixture in the resin composition (effect of finely emulsifying and dispersing the polyphenylene ether resin in the polypropylene resin) is not preferable. Moreover, since it will be inferior to a linear expansion coefficient and a rigidity fall will become remarkable when a compounding quantity exceeds 30 mass parts, it is unpreferable.

  Next, the blending amount of the component (d) is preferably 0 to 30 parts by mass, more preferably 100 parts by mass with respect to the total of 100 parts by mass of the component (a) and the component (b) from the viewpoint of rigidity and heat resistance. Is 1-20 parts by mass. When the blending amount of component (d) exceeds 30 parts by mass, the rigidity and heat resistance are significantly lowered, which is not preferable.

  Moreover, the total compounding quantity of (e) component and (f) component is 40-140 mass parts with respect to a total of 100 mass parts of (a) component and (b) component. When the total amount of the component (e) and the component (f) is less than 40 parts by mass, the fluidity is excellent, but the rigidity and linear expansion are inferior. A blending amount exceeding 140 parts by mass is not preferable because it is excellent in rigidity and linear expansion but inferior in fluidity.

  The mass ratio of the component (e) and the component (f) is preferably 80/20 to 20/80, and more preferably 30/70 to 70/30. By setting the mass ratio within the above range, the balance of rigidity, linear expansion coefficient, and anisotropy tends to be better.

  In the present embodiment, in addition to the above-mentioned components, other additional components, for example, a vinyl aromatic compound-conjugated diene compound block copolymer, as necessary, within a range not impairing the effects of the present embodiment. And olefin elastomers, antioxidants, metal deactivators, heat stabilizers, flame retardants (organophosphate compounds, ammonium polyphosphate compounds, melamine polyphosphate compounds, phosphinates, magnesium hydroxide, aromatic Group halogen flame retardants, silicone flame retardants, etc.), fluoropolymers, plasticizers (low molecular weight polyethylene, epoxidized soybean oil, polyethylene glycol, fatty acid esters, etc.), flame retardant aids such as antimony trioxide, weather resistance ( Light) improver, polyolefin nucleating agent, slip agent, inorganic or organic filler or reinforcing material (GF long fiber, CF long fiber) Polyacrylonitrile fibers, carbon black, titanium oxide, calcium carbonate, conductive metal fibers, conductive carbon black, etc.), various colorants, may be added such as mold release agents.

  The resin composition of the present embodiment is obtained by melt-kneading the components (a) to (f) or the components (a) to (c), (e) and (f). The melt kneader is not particularly limited, and a known kneader can be used. For example, a single screw extruder, a multi-screw extruder including a twin screw extruder, a roll, a kneader, a Brabender plastograph, a Banbury mixer And the like. Among these, the melt kneading method using a twin screw extruder is preferable. Specifically, the ZSK series manufactured by Coperion, the TEM series manufactured by Toshiba Machine Co., Ltd., the TEX series manufactured by Nippon Steel Works, Ltd., and the like can be used.

  Moreover, if it is a case where an extruder is used, the kind, specification, etc. will not be specifically limited, A well-known extruder can be used suitably. The L / D (barrel effective length / barrel inner diameter) of the extruder is preferably in the range of 20 to 75, more preferably in the range of 30 to 60.

  The extruder has a first raw material supply port on the upstream side with respect to the flow direction of the raw material, a first vacuum vent on the downstream side, a second raw material supply port on the downstream side, and a second vacuum vent on the downstream side. In addition, it is preferable to provide a first raw material supply port on the upstream side, a first vacuum vent on the downstream side, a second and third raw material supply port on the downstream side, and a second vacuum vent on the downstream side.

  Among these, 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 further between the second raw material supply port and the second vacuum vent. A kneading section is provided, 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 a second raw material supply port and a third More preferably, a kneading section is provided at the raw material supply port, and a kneading section is provided between the second raw material supply port and the second vacuum vent.

  Moreover, the raw material supply method to a 2nd, 3rd raw material supply port is not specifically limited, Rather than the mere addition supply from the open port of the 2nd, 3rd raw material supply port of an extruder, it is from an extruder side open port. It is more stable and preferable to supply using a forced side feeder.

  (A)-(f) component, or (a)-(c) component, (e), (f) As a method of melt-kneading a component, using the twin-screw extruder which has several feed ports, the following A method comprising the steps (1) and (2) is preferred.

(1) a step of melt-kneading a total amount of the component (b), a component (c), a part or the total amount of the component (d), and a part of the component (a);
(2) A step of melt-kneading the remaining amount of the component (a), the component (c), and the component (d) with respect to the kneaded product obtained in the step (1).

  The component (e) and the component (f) may be introduced from any feed port.

Alternatively, as a method of melt kneading the components (a) to (f), or the components (a) to (c), (e), and (f), the following steps (1) and (2) are performed. The method of including is also preferable.
(1) a step of melt-kneading the total amount of the component (b), the component (c), and a part or the total amount of the component (d);
(2) A step of adding the total amount of the component (a) and the remaining amount of the components (c) and (d) to the kneaded product obtained in the step (1) and melt-kneading.

  The component (e) and the component (f) may be introduced from any feed port.

  The melt-kneading temperature and the screw rotation speed are not particularly limited, but can be appropriately selected from a melt-kneading temperature of 200 to 370 ° C. and a screw rotation speed of 100 to 1200 rpm.

  The resin composition of the present embodiment can be molded as various parts molded articles, sheets, or films by various conventionally known methods such as injection molding, extrusion molding, extrusion profile forming, and hollow molding. Examples of these various parts include automobile parts. Specifically, bumpers, fenders, door panels, various moldings, emblems, engine hoods, wheel caps, roofs, spoilers, various aero parts, etc. Suitable for interior parts such as instrument panels, console boxes and trims.

  Furthermore, it can also be used suitably as an interior / exterior part of electrical equipment, specifically, various computers and peripheral equipment, other OA equipment, televisions, videos, various disk player cabinets, chassis, refrigerators, air conditioners, liquid crystals. Projector. It is also suitable for a lithium ion battery separator for electrical equipment. Industrial use is suitable for parts such as various pump casings and boiler casings.

Next, the present embodiment will be described more specifically with reference to examples and comparative examples. However, the present embodiment is not limited to the following examples unless it exceeds the gist.
Each physical property of each material was measured as follows.
[Number average molecular weight]
The number average molecular weight of each component was measured by GPC (mobile phase: tetrahydrofuran, standard substance: polystyrene). As a measuring instrument, Shimadzu LC-10 was used.

[Measurement of bound styrene content]
The amount of bound styrene was measured by NMR. JNM JNM-LA400 was used as a measuring instrument.

[Measurement of total vinyl bond content]
The total vinyl bond amount was measured with an infrared spectrophotometer. As a measuring instrument, FT / IR-230 manufactured by JASCO Corporation was used.

[Measurement of hydrogenation rate]
The hydrogenation rate was measured by NMR. As a measuring instrument, DPX-400 manufactured by BRUKER was used.

[Melting point]
The melting point of each component was measured with a differential scanning calorimeter.

[MFR (melt flow rate)]
MFR was measured under the conditions of 230 ° C. and a load of 2.16 kg. As a measuring device, Toyo Seiki P-111 was used.

[Reduced viscosity]
The reduced viscosity was measured under conditions of 0.5 g / dL chloroform solution and 30 ° C. As a measuring instrument, an Ubbelohde viscosity tube was used.

[Average fiber length and average fiber diameter]
The average fiber length L and the average fiber diameter D of the fibrous filler were determined as follows.
The fibrous filler was dispersed in water, transferred onto a slide glass, and observed under an optical microscope. Using an image analysis apparatus, the length of 400 arbitrarily selected fibrous fillers was measured and determined by the following formula.
Average fiber diameter D = ΣLi / n (number average)
Average fiber length L = ΣLi ² / ΣLi (weight average)
Here, in the formula, Li indicates the length of each fibrous filler (L1, L2,..., L400), and Li ² indicates the length of each corresponding fibrous filler. Square (L1 ² , L2 ² ,..., L400 ² ), n represents the number of observed fibrous fillers.

[Average particle size]
The average particle diameter of the inorganic filler was measured by a centrifugal sedimentation light transmission method.

[Production of resin composition]
1. Component (a) (polypropylene resin)
(A-1) Propylene homopolymer Melting point: 167 ° C., MFR: 0.5 g / 10 min (a-2) Propylene homopolymer Melting point: 164 ° C., MFR: 75 g / 10 min

2. Component (b) (polyphenylene ether resin)
(B-1) 2,6-xylenol was oxidatively polymerized to obtain a polyphenylene ether homopolymer.
Reduced viscosity: 0.31
(B-2) 2,6-xylenol was oxidatively polymerized to obtain a polyphenylene ether homopolymer.
Reduced viscosity: 0.42

3. Component (c) (hydrogenated block copolymer)
A block copolymer having a B-A-B-A type structure of hydrogenated polybutadiene-polystyrene (1) -hydrogenated polybutadiene-polystyrene (2) was synthesized by a conventional method. This block copolymer was hydrogenated by a conventional method to obtain a hydrogenated block copolymer.
Bonded styrene content: 43% by mass
Total amount of 1,2-vinyl bonds and 3,4-vinyl bonds in polybutadiene before hydrogenation (total vinyl bonds): 75%
Number average molecular weight of hydrogenated block copolymer: 98000
Number average molecular weight of polystyrene (1): 20000
Number average molecular weight of polystyrene (2): 22000
Polybutadiene part hydrogenation rate: 99.9%

4). Component (d) (hydrogenated block copolymer)
A block copolymer having a B-A-B-A type structure of hydrogenated polybutadiene-polystyrene (1) -hydrogenated polybutadiene-polystyrene (2) was synthesized by a conventional method. This block copolymer was hydrogenated by a conventional method to obtain a hydrogenated block copolymer.
Bonded styrene content: 60% by mass
Total amount of 1,2-vinyl bonds and 3,4-vinyl bonds in polybutadiene before hydrogenation (total vinyl bonds): 36%
Number average molecular weight of hydrogenated block copolymer: 113000
Number average molecular weight of polystyrene (1): 34000
Number average molecular weight of polystyrene (2): 34000
Polybutadiene part hydrogenation rate: 99.9%

5. (E) Component (Wollastonite)
(E-1) Wollastonite Average fiber diameter 8 μm Aspect ratio 13
(E-2) Wollastonite Average fiber diameter 8 μm Aspect ratio 3

6). (F) component (inorganic filler)
(F-1) Kaolin clay Average particle diameter 0.2 μm Surface treatment: None (f-2) Talc Average particle diameter 0.8 μm Surface treatment: None (f-3) Calcium carbonate 0.15 μm Surface treatment: None

[Examples 1-6 and Comparative Examples 1-6]
<Example 1>
Using a twin-screw extruder ZSK-25 (manufactured by Coperion), a first raw material supply port is provided upstream of the raw material flow direction, a second raw material supply port is provided downstream of this, and a vacuum vent is further provided downstream thereof. It was. Moreover, the raw material supply method to the 2nd supply port supplied using the forced side feeder from the extruder side open port. Using the extruder set as described above, the components (a) to (f), or the components (a) to (c), the components (e) and (f) are the compositions (parts by mass) shown in Table 1. The resulting mixture was melt kneaded under conditions of an extrusion temperature of 270 to 320 ° C., a screw rotation speed of 300 rpm, and a discharge rate of 15 kg / hour to obtain pellets.

<Examples 2 to 6>
Pellets were obtained in the same manner as in Example 1 except that the components (a) to (f) were performed under the conditions shown in Table 1.

<Comparative Examples 1, 5, 6>
Pellets were obtained in the same manner as in Example 1 except that the components (a) to (f) were performed under the conditions shown in Table 1.

<Comparative Examples 2-4>
Pellets were obtained in the same manner as in Example 1, but the extrudability was poor (poor bite between component (e) and component (f)) and pellets could not be obtained.

The bending elastic modulus and linear expansion coefficient were measured as follows, and the rigidity, thermal rigidity retention, linear expansion coefficient, and anisotropy were evaluated.
<Bending elastic modulus>
The resin pellet obtained above is supplied to a screw in-line type injection molding machine set at 220 to 280 ° C., and a test piece for measuring the flexural modulus is injection molded at a mold temperature of 60 ° C. The heat history process was performed by leaving it to stand in an environment of 80 ° C. for 24 hours. Using these molded articles, the flexural modulus was measured according to ISO 178 (measurement temperature: 23 ° C., 90 ° C.). The thermal stiffness retention was expressed as a percentage with respect to 23 ° C. (thermal stiffness retention (%) = flexural modulus 90 ° C./flexural modulus 23 ° C. × 100).

<Linear expansion coefficient>
Using the resin pellet obtained above, it is supplied to a screw in-line type injection molding machine set at 220 to 280 ° C., and under the condition of a mold temperature of 60 ° C., a test piece for linear expansion measurement (flat plate shaped piece 90 mm × 50 mm × 2.5 mm) was injection-molded and allowed to stand in an environment of 120 ° C. for 1 hour using a gear oven to perform a heat history treatment. After the heat treatment, the test piece was cut out from the center of the test piece in the flow direction (MD) and the right-angle direction (TD) to a length of 10 mm, respectively, and the coefficient of linear expansion in the range of -30 to 120 ° C. was measured with a thermal analyzer (TMA) (Perkin Elmer TMA-7, Inc., temperature rising rate = 5 ° C./min). Anisotropy was evaluated by TD / MD.
The above results are also shown in Table 1.

  From the result of Table 1, it turned out that the resin composition (Examples 1-6) of this Embodiment is excellent in rigidity, thermal rigidity retention, a linear expansion coefficient, and anisotropy simultaneously. Moreover, when the composition of the resin composition is out of the range of the present embodiment (Comparative Examples 1 to 6), the rigidity, thermal rigidity retention, linear expansion coefficient, and anisotropy cannot be improved at the same time. I understood.

  Since the resin composition of the present invention is excellent in the balance of the rigidity, thermal rigidity retention rate, linear expansion coefficient, and anisotropy of a molded product, it has industrial applicability to applications requiring these characteristics.

Claims (11)

(A) 20 to 99 parts by mass of a polypropylene resin,
(B) 80-1 parts by mass of a polyphenylene ether resin,
(C) vinyl aromatic compound-conjugated diene compound block co-polymer weight of (c) bonded vinyl aromatic compound is 15% by mass or more and 45% by mass or less with respect to 100 parts by mass in total of component (a) and component (b). 1-30 parts by mass of combined hydrogenated product,
A vinyl aromatic compound-conjugated diene compound block in which the amount of (d) bonded vinyl aromatic compound exceeds 45% by mass and is 95% by mass or less with respect to 100 parts by mass in total of the component (a) and the component (b). 0-30 parts by weight of hydrogenated copolymer
(E) fibrous filler,
(F) at least one inorganic filler selected from the group consisting of kaolin clay, talc, and calcium carbonate, having an average particle size of 1 μm or less,
The resin composition whose sum total of the said (e) component and the said (f) component is 40-140 mass parts with respect to 100 mass parts in total of the said (a) component and the said (b) component.   The resin composition of Claim 1 whose melt flow rate (MFR) (230 degreeC, load 2.16Kg) of the polypropylene resin of said (a) component is 0.1-150 g / 10min.   The component (c) is a hydrogenated styrene-butadiene block copolymer, and the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds in the butadiene polymer block is 65 to 90%. The resin composition according to claim 1 or 2.   The resin composition according to any one of claims 1 to 3, wherein the component (d) is a hydrogenated product of a styrene-butadiene block copolymer.   The resin composition according to any one of claims 1 to 4, wherein a mass ratio of the component (e) / the component (f) is 80/20 to 20/80.   The resin composition according to claim 1, wherein the component (e) is one or more selected from the group consisting of glass fiber, carbon fiber, metal fiber, inorganic fiber, and wollastonite.   The component (e) is a wollastonite having an average fiber diameter D of 1 to 30 μm, an average fiber length L of 10 to 500 μm, and an aspect ratio (L / D) of 4 to 30. The resin composition according to Item.   The resin composition according to claim 1, wherein the component (f) is kaolin clay.   The resin composition according to claim 1, wherein the component (a) forms a matrix phase and the component (b) forms a dispersed phase.   A molded article comprising the resin composition according to any one of claims 1 to 9.   The molded article according to claim 10, which is an automotive exterior part.