Resin composition and molded article

Abstract

The present invention relates to a resin composition and a molded article. A resin composition comprising (a) a polyphenylene ether-based resin, (b) a polypropylene-based resin, (c) a mixing agent, (d) an inorganic filler, (e) a hydrotalcite-like compound, and (f) a polyolefin modified with an unsaturated carboxylic acid, the (c) mixing agent being one or more selected from the group consisting of a hydrogenated block copolymer obtained by hydrogenating at least a portion of a block copolymer comprising a polymer block a of a vinyl aromatic compound as a main component and a polymer block b of a conjugated diene compound as a main component, a copolymer having a polystyrene block chain-polyolefin block chain, and a copolymer having a polyphenylene ether block chain-polyolefin block chain, the (d) inorganic filler comprising an inorganic filler surface-treated with a surface treatment agent containing an acid functional group.

Description

[0001] This application is a divisional application. The international application number of the original application is PCT / JP2020 / 019497, the international application date is May 15, 2020, the Chinese national application number is 202080032500.7, the entry date into China is October 29, 2021, and the invention title is "Resin Composition and Molded Article". Technical Field

[0002] This invention relates to resin compositions and molded articles. Background Technology

[0003] Polypropylene resin exhibits excellent molding processability, water resistance, oil resistance, acid resistance, and alkali resistance, but suffers from poor heat resistance, rigidity, and impact resistance. Therefore, polyphenylene ether resin is blended into this polypropylene resin, forming the polypropylene resin matrix and the polyphenylene ether resin dispersed into particles, thereby creating a resin composition with improved heat resistance and rigidity.

[0004] As such prior art, for example, Patent Document 1 describes a technique for improving solvent resistance and impact resistance by blending polyphenylene ether with polyolefin, and Patent Documents 2 and 3 describe techniques for improving impact resistance by blending polyphenylene ether with polyolefin and hydrogenated block copolymer.

[0005] In addition, patent documents 4 to 9 describe techniques for obtaining resin compositions with excellent chemical resistance and processability by blending specific hydrogenated block copolymers into a resin composition composed of polyolefin resin and polyphenylene ether resin.

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: US Patent No. 3361851

[0009] Patent Document 2: US Patent No. 4,383,082

[0010] Patent Document 3: European Patent Application Publication No. 0115712

[0011] Patent Document 4: Japanese Patent Application Publication No. 63-113058

[0012] Patent Document 5: Japanese Patent Application Publication No. 63-225642

[0013] Patent Document 6: US Patent No. 4,863,997

[0014] Patent Document 7: Japanese Patent Application Publication No. 3-72512

[0015] Patent Document 8: Japanese Patent Application Publication No. 4-183748

[0016] Patent Document 9: Japanese Patent Application Publication No. 5-320471 Summary of the Invention

[0017] The problem that the invention aims to solve

[0018] Alloys of polypropylene and polyphenylene ether resins are used in automotive parts and water-using components. Water-using components are expected to operate under water pressure and high temperature conditions, thus requiring heat resistance, water resistance, impact resistance, rigidity, and vibration fatigue resistance, necessitating inorganic filler reinforcement materials.

[0019] However, for alloy materials of polypropylene and polyphenylene ether resins, it is clear that although they have excellent water resistance, the interface between the inorganic filler and the resin is not resistant to water and acid, and their physical properties will be reduced due to immersion in water and acid.

[0020] That is, the existing polypropylene / polyphenylene ether resin compositions proposed in Patent Documents 1 to 9 still have problems in terms of water resistance when glass fibers are added.

[0021] Therefore, the object of the present invention is to provide a polypropylene / polyphenylene ether resin composition that exhibits excellent water resistance even when inorganic fillers are added.

[0022] Methods for solving problems

[0023] In order to solve the above problems, the inventors conducted in-depth research and found that by adding a hydrotalcite-like compound to the polypropylene / polyphenylene ether composition, the decrease in physical properties in water when inorganic fillers are added can be mitigated. Furthermore, it was found that by adding a hydrotalcite-like compound to the polypropylene / polyphenylene ether composition, excellent water resistance can be obtained even when inorganic fillers are added, which was previously not possible. Thus, the present invention was completed.

[0024] That is, the present invention is as follows. [1]

[0026] A resin composition comprising (a) a polyphenylene ether resin, (b) a polypropylene resin, (c) a mixture, (d) an inorganic filler, and (e) a hydrotalcite compound. [2]

[0028] The resin composition as described in [1] further comprises (f) a polyolefin modified with unsaturated carboxylic acid. [3]

[0030] The resin composition as described in [1] or [2], wherein the unnotched chevron impact strength is 10 kJ / m 2 above. [4]

[0032] The resin composition as described in any one of [1] to [3], wherein the inorganic filler in (d) comprises glass fiber. [5]

[0034] The resin composition as described in any one of [1] to [4], wherein the inorganic filler of (d) comprises a fibrous filler with a fiber diameter of 11 to 20 μm. [6]

[0036] The resin composition as described in any one of [1] to [5], wherein the inorganic filler of the above (d) comprises an inorganic filler that has been surface-treated with a surface treatment agent containing acid functional groups. [7]

[0038] The resin composition as described in any one of [1] to [6], wherein the particle size of the above-mentioned (e) type hydrotalcite compound is 1 nm or more and 2 μm or less. [8]

[0040] The resin composition as described in any one of [1] to [7], wherein the specific viscosity of the polyphenylene ether resin (a) is 0.35 dL / g or higher. [9]

[0042] The resin composition as described in any one of [1] to [8], wherein the above-mentioned (c) mixture is one or more selected from the group consisting of hydrogenated block copolymers, copolymers having polystyrene block chains and polyolefin block chains, and copolymers having polyphenylene ether block chains and polyolefin block chains.

[10]

[0044] The resin composition as described in any one of [1] to [9], wherein the hydrogenation rate of the above-mentioned (c) mixture is 90% or more.

[11]

[0046] The resin composition as described in any one of [1] to

[10] , wherein the vinyl binding content of the mixture in (c) above is greater than 50%.

[12]

[0048] The resin composition as described in any one of [1] to

[11] , wherein the phosphorus content is 0.3% by mass or less.

[13]

[0050] The resin composition as described in any one of [1] to

[12] , wherein the phase forming dispersed phase comprises the polyphenylene ether resin described above (a) and the phase forming matrix phase comprises the polypropylene resin described above (b).

[14]

[0052] The resin composition as described in

[13] , wherein the phase comprising the above-mentioned (a) polyphenylene ether resin has an average short axis diameter of 10 nm or more and 1 μm or less.

[15]

[0054] The resin composition as described in

[13] or

[14] , wherein, in 10 or more of the 100 phases comprising the polyphenylene ether resin described above (a), a linear phase comprising the mixture described above (c) with a length of 75 nm or more is located inside the phase comprising the polyphenylene ether resin described above (a).

[16]

[0056] A molded article formed by molding the resin composition described in any one of [1] to

[15] .

[17]

[0058] Molded articles as described in

[16] are automotive electrical / electronic components or water-using components.

[0059] The effects of the invention

[0060] According to the present invention, a polypropylene / polyphenylene ether resin composition with excellent water resistance can be obtained even when inorganic fillers are added. Attached Figure Description

[0061] Figure 1 The image is obtained by observing the following situation in the resin composition of Example 2 using TEM: in more than 10 of the 100 phases containing component (a), the linear phase containing the mixture of (c) with a length of 75 nm or more is dispersed in a state inside the phase containing component (a).

[0062] Figure 2 The image is obtained by observing the following situation in the resin composition of Example 24 using TEM: in more than 10 of the 100 phases containing component (a), the linear phase containing the mixture of (c) with a length of 75 nm or more is dispersed in a state inside the phase containing component (a).

[0063] Figure 3 The image was obtained by observing the following situation in the resin composition of Comparative Example 19 using TEM: in more than 10 of the 100 phases containing component (a), the linear phase containing the mixture of component (c) with a length of 75 nm or more is dispersed in a state that is not inside the phase containing component (a).

[0064] Figure 4The image was obtained by observing the following situation in the resin composition of Comparative Example 3 using TEM: in more than 10 of the 100 phases containing component (a), the linear phase containing the mixture of component (c) with a length of 75 nm or more is dispersed in a state that is not inside the phase containing component (a). Detailed Implementation

[0065] The specific embodiments of the present invention (hereinafter referred to as "this embodiment") are described in detail below. It should be noted that the present invention is not limited to the following embodiments, and various modifications can be made within the scope of its key points.

[0066] [Resin Composition]

[0067] The resin composition of this embodiment is a composition comprising (a) a polyphenylene ether resin, (b) polypropylene, (c) a mixture, (d) glass fiber, and (e) a hydrotalcite-like compound.

[0068] By adopting the above-described configuration, the resin composition of this embodiment can obtain a polypropylene / polyphenylene ether resin composition with excellent water resistance even when inorganic fillers are added, thereby achieving a balance of water resistance, heat resistance, impact resistance, rigidity, and vibration fatigue characteristics of the molded article.

[0069] [(a) Polyphenylene ether resin]

[0070] Specific examples of polyphenylene ether-based resins in embodiment (a) include 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 copolymers of 2,6-dimethylphenol with other phenols (e.g., copolymers with 2,3,6-trimethylphenol and copolymers with 2-methyl-6-butylphenol as described in Japanese Patent Publication No. 52-17880). Among these, polyphenylene ethers particularly preferred are copolymers of poly(2,6-dimethyl-1,4-phenylene ether), copolymers of 2,6-dimethylphenol and 2,3,6-trimethylphenol, or mixtures thereof.

[0071] (a) There is no particular limitation on the manufacturing method of the component, as long as it is obtained by a known method, such as the manufacturing methods described in U.S. Patent No. 3,306,874, U.S. Patent No. 3,306,875, U.S. Patent No. 3,257,357 and U.S. Patent No. 3,257,358, Japanese Patent Application Publication No. 50-51,197, Japanese Patent Application Publication No. 52-17,880 and Japanese Patent Application Publication No. 63-152,628.

[0072] In this embodiment, the lower limit of the preferred range for the specific viscosity (0.5 g / dL chloroform solution, 30°C, measured using an Ubbelohde viscometer) of component (a) is 0.30 dL / g, more preferably 0.032 dL / g, and even more preferably 0.035 dL / g. Furthermore, the upper limit of this preferred range for specific viscosity is 0.80 dL / g, more preferably 0.75 dL / g, and even more preferably 0.55 dL / g. When the specific viscosity of (a) polyphenylene ether is within this range, it exhibits excellent impact resistance, heat resistance, and other properties, and is therefore preferred.

[0073] In the component (a) of this embodiment, even blends of two or more polyphenylene ethers with different specific viscosities can be used.

[0074] In addition, various known stabilizers can be appropriately used for the stabilization of polyphenylene ether. Examples of stabilizers include metal stabilizers such as zinc oxide and zinc sulfide, hindered phenolic stabilizers, phosphorus stabilizers, hindered amine stabilizers, and other organic stabilizers, with a preferred mixing amount of less than 5 parts by mass relative to 100 parts by mass of component (a).

[0075] In addition, known additives that can be added to polyphenylene ether can be added in an amount of less than 10 parts by mass relative to 100 parts by mass of component (a).

[0076] [(b) Polypropylene resins]

[0077] (b) Polypropylene resins are not particularly limited, for example, homopolymers and / or copolymers with propylene as the repeating unit structure, preferably crystalline propylene homopolymers, crystalline propylene-ethylene block copolymers, and mixtures of crystalline propylene homopolymers and crystalline propylene-ethylene block copolymers.

[0078] There is no particular limitation on what constitutes a crystalline propylene-ethylene block copolymer; for example, substances having a crystalline propylene homopolymer portion and a propylene-ethylene random copolymer portion can be cited.

[0079] From the perspective of suppressing dripping during combustion and improving the balance between fluidity and mechanical strength of the resin composition, the melt mass flow rate (hereinafter also referred to as "MFR") of component (b) is preferably 0.1 g / 10 min or more, more preferably 0.3 g / 10 min or more, particularly preferably 0.5 g / 10 min or more, and preferably 15 g / 10 min or less, more preferably 6 g / 10 min or less, particularly preferably 3 g / 10 min or less.

[0080] It should be noted that the MFR can be determined according to ISO 1133 at a temperature of 230°C and a load of 2.16 kg. Specifically, the MFR can be determined by the method described in the examples below.

[0081] The manufacturing method for component (b) is not particularly limited, and known components can be used. Specific examples of methods for manufacturing polypropylene include methods for polymerizing propylene at temperatures of 0–100°C and pressures of 3–100 atmospheres in the presence of a polymerization catalyst composition (which includes a titanium trichloride catalyst or a titanium halide catalyst supported on a support such as magnesium chloride, and contains an alkyl aluminum compound). In the above methods, chain transfer agents such as hydrogen can be added to adjust the molecular weight of the polymer.

[0082] Furthermore, in the above method, in addition to the polymerization catalyst composition described above, the polymerization system may further contain an electron-donating compound as an internal or external donor component in order to improve the isotactic regularity of the obtained polypropylene and the polymerization activity of the polymerization system. There are no particular limitations on these electron-donating compounds, and known substances can be used. Specific examples of electron-donating compounds include ester compounds such as ε-caprolactone, methyl methacrylate, ethyl benzoate, and methyl methyl benzoate; phosphites such as triphenyl phosphite and tributyl phosphite; phosphoric acid derivatives such as hexamethylphosphoryltriamine; alkoxy ester compounds; aromatic monocarboxylic acid esters; aromatic alkyl alkoxysilanes; aliphatic hydrocarbon alkoxysilanes; various ether compounds; various alcohols; and various phenols.

[0083] The polymerization method described above can be either batch polymerization or continuous polymerization. The polymerization method can be solution polymerization and slurry polymerization using solvents such as butane, pentane, hexane, heptane, and octane; as well as bulk polymerization in monomers under solvent-free conditions and gas-phase polymerization in gaseous polymers.

[0084] In the manufacturing method of component (b), particularly the manufacturing method of the crystalline propylene-ethylene block copolymer, there is no particular limitation. For example, a method including the first and second steps described below can be cited. In the first step, a crystalline propylene homopolymer portion is obtained. In the second step, the crystalline propylene homopolymer portion is copolymerized with ethylene and other α-olefins added as needed, thereby obtaining the propylene-ethylene block copolymer portion combined with the crystalline propylene homopolymer portion. Here, other α-olefins are not particularly limited, and examples include propylene, 1-butene, and 1-hexene.

[0085] In this embodiment, the total content of component (a) and component (b) is 30% by mass or more, preferably 35% by mass or more, more preferably 40% by mass or more, and preferably 80% by mass or less, preferably 75% by mass or less, more preferably 70% by mass or less, from the perspective of the impact resistance and production stability of the resin composition.

[0086] [(a) The ratio of polyphenylene ether resin to (b) polypropylene]

[0087] In this embodiment, regarding the preferred content ratio of component (a) and component (b), when the total amount of component (a) and component (b) is 100 parts by mass, the content of component (a) is 10 to 70 parts by mass and the content of component (b) is 30 to 90 parts by mass. More preferably, the content of component (a) is 10 to 60 parts by mass and the content of component (b) is 40 to 90 parts by mass. Even more preferably, the content of component (a) is in the range of 10 to 50 parts by mass and the content of component (b) is 50 to 90 parts by mass. When the content ratio of component (a) to component (b) is within this range, the balance of impact resistance, heat resistance, and tensile strength is excellent, which is preferred.

[0088] It should be noted that these proportions in the resin composition can be determined using Fourier transform infrared spectroscopy (FT-IR) via the calibration curve method.

[0089] [(c) Mixture]

[0090] The resin composition of this embodiment, by containing the mixture (c), can form a matrix phase containing component (b) and a dispersed phase containing component (a). This further improves the heat creep resistance of the obtained resin composition.

[0091] As component (c), a copolymer having both highly compatible segmental block chains with respect to component (a) and highly compatible segmental block chains with respect to component (b) is preferred. High compatibility simply means that phase separation has not occurred.

[0092] Examples of highly compatible segmental blocks for component (a) include polystyrene segmental blocks and polyphenylene ether segmental blocks.

[0093] Examples of highly compatible segmental block chains for component (b) include polyolefin block chains and copolymer elastomer block chains of ethylene and α-olefins.

[0094] It should be noted that in this specification, component (c) is not included in the scope of components (a) and (b).

[0095] As component (c), examples include one or more selected from the group consisting of hydrogenated block copolymers, copolymers having polystyrene block chains and polyolefin block chains, and copolymers having polyphenylene ether block chains and polyolefin block chains. Among these, hydrogenated block copolymers are preferred from the viewpoint of superior thermal stability. Component (c) may be used alone or in combination of two or more.

[0096] Examples of hydrogenated block copolymers include hydrogenated block copolymers formed by hydrogenating at least a portion of 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.

[0097] As a preferred specific example of a hydrogenated block copolymer, a preferred example is a hydrogenated 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 with a total 1,2-vinyl and 3,4-vinyl content of 30-90%. From the perspective of compatibility with polyphenylene ether resins and vibration fatigue characteristics, the total 1,2-vinyl and 3,4-vinyl content of the conjugated diene compound in polymer block b is preferably 30-90%.

[0098] Polymer block a is preferably a homopolymer block of a vinyl aromatic compound or a copolymer block of a vinyl aromatic compound and a conjugated diene compound.

[0099] "Mainly composed of vinyl aromatic compounds" in polymer block a means that polymer block a contains more than 50% by mass of vinyl aromatic compound units. Furthermore, from the perspective of superior molding flowability, impact resistance, weld lines, and appearance, it is preferable that polymer block a contains more than 70% by mass of vinyl aromatic compound units.

[0100] Examples of vinyl aromatic compounds constituting polymer block a include styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, and diphenylethylene. Styrene is preferred.

[0101] These ingredients can be used alone or in combination with two or more.

[0102] The number-average molecular weight of polymer block a is not particularly limited, but is preferably 15,000 or more, and more preferably 50,000 or less. By setting the number-average molecular weight of polymer block a within the above range, the impact resistance of the resin composition of this embodiment can be made more excellent.

[0103] The number-average molecular weight of polymer block a can be determined by GPC (mobile phase: chloroform, standard substance: polystyrene).

[0104] Polymer block b is preferably a homopolymer block of a conjugated diene compound or a random copolymer block of a conjugated diene compound and a vinyl aromatic compound.

[0105] "Conjugated diene compound as the main component" in polymer block b means that polymer block b contains more than 50% by mass of conjugated diene compound units. Furthermore, from the perspective of superior molding flowability, impact resistance, weld lines, and appearance, it is preferable that polymer block b contains more than 70% by mass of conjugated diene compound units.

[0106] Examples of conjugated diene compounds constituting polymer block b include butadiene, isoprene, 1,3-pentadiene, and 2,3-dimethyl-1,3-butadiene. Butadiene, isoprene, and combinations thereof are preferred.

[0107] These ingredients can be used alone or in combination of two or more.

[0108] Regarding the microstructure of polymer block b (the binding morphology of the conjugated diene compound), the total amount of 1,2-vinyl binding and 3,4-vinyl binding (hereinafter sometimes referred to as "total vinyl binding") is preferably 30-90%, more preferably 45-90%, and even more preferably 65-90%, relative to the total amount of vinyl binding contained in the conjugated diene compound constituting the polymer block.

[0109] By ensuring the total vinyl content of the conjugated diene compound in polymer block b is within the aforementioned range, the compatibility with polypropylene resins is further improved. In particular, by ensuring the total vinyl content is 30% or more, the dispersibility of component (a) in the resin composition is further improved. By ensuring the total vinyl content is 90% or less, the excellent dispersibility of component (a) can be maintained, and the economy is also excellent.

[0110] Especially when polymer block b is a butadiene-based polymer block, the total vinyl binding content of butadiene in polymer block b is preferably 65-90%.

[0111] The total vinyl binding amount can be determined using an infrared spectrophotometer. The calculation method can be performed according to the method described in Analytical Chemistry, Volume 21, No. 8, August 1949.

[0112] (c) is preferably a hydrogenated block copolymer containing at least polymer block a and polymer block b. When polymer block a in (c) is represented as "a" and polymer block b as "b", examples of components (c) include hydrogenated vinyl aromatic compound-conjugated diene compound block copolymers having structures such as ab, aba, baba, (ab-)4Si, and ababa. The Si in (ab-)4Si can be a reaction residue of a multifunctional coupling agent such as silicon tetrachloride or tin tetrachloride, or a residue of an initiator such as a multifunctional organolithium compound.

[0113] The molecular structure of the block copolymer containing polymer block a and polymer block b is not particularly limited, and can be linear, branched, radial, or any combination thereof.

[0114] Regarding polymer block a and polymer block b, the distribution of vinyl aromatic compounds or conjugated diene compounds in the molecular chain of each polymer block can be random, variable (where monomer components increase or decrease along the molecular chain), partially blocky, or any combination thereof.

[0115] If there are more than two of either polymer block a or polymer block b in the repeating unit, these two or more polymer blocks can be the same structure or different structures.

[0116] (c) In the hydrogenated block copolymer of component (c), from the perspective of superior molding flowability, impact resistance, weld lines, and appearance, the structural units derived from vinyl aromatic compounds contained in the unhydrogenated block copolymer are preferably 20 to 95% by mass. The lower limit of the content of the above structural units can be 30% by mass or more, 40% by mass or more, 50% by mass or more, or 60% by mass or more, and the upper limit can be 85% by mass or less, 75% by mass or less, 65% by mass or less, or 55% by mass or less.

[0117] It should be noted that the content of structural units from vinyl aromatic compounds can be determined using an ultraviolet spectrophotometer.

[0118] The number-average molecular weight (Mn) of the block copolymer before hydrogenation is preferably 5,000 to 1,000,000. The lower limit of the number-average molecular weight (Mn) can be 10,000 or more, 20,000 or more, 40,000 or more, or 60,000 or more, and the upper limit can be 800,000 or less, 500,000 or less, 200,000 or less, 100,000 or less, or 80,000 or less.

[0119] It should be noted that the number average molecular weight (Mn) can be determined by gel permeation chromatography (GPC, mobile phase: chloroform, standard substance: polystyrene).

[0120] The molecular weight distribution of the block copolymer before hydrogenation is preferably below 10. The molecular weight distribution can be calculated as follows: the ratio (Mw / Mn) of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn) is determined using GPC (GPC, mobile phase: chloroform, standard substance: polystyrene), and the molecular weight distribution is calculated accordingly.

[0121] (c) The hydrogenation rate of the double bond from the conjugated diene compound in the component is not particularly limited, but from the perspective of better heat resistance, it is preferably 50% or more, more preferably 80% or more, and even more preferably 90% or more.

[0122] It should be noted that the hydrogenation rate can be determined by NMR.

[0123] (c) The method for manufacturing the hydrogenated block copolymer of component (c) is not particularly limited, and known manufacturing methods may be used. Examples of manufacturing methods described in Japanese Patent Application Publication No. 47-011486, Japanese Patent Application Publication No. 49-066743, Japanese Patent Application Publication No. 50-075651, Japanese Patent Application Publication No. 54-126255, Japanese Patent Application Publication No. 56-010542, Japanese Patent Application Publication No. 56-062847, Japanese Patent Application Publication No. 56-100840, Japanese Patent Application Publication No. 02-300218, British Patent No. 1130770, US Patent No. 3281383, US Patent No. 3639517, British Patent No. 1020720, US Patent No. 3333024, and US Patent No. 4501857 are examples.

[0124] (c) The hydrogenated block copolymer of component can be a modified hydrogenated block copolymer obtained by grafting or adding the above hydrogenated block copolymer with α,β-unsaturated carboxylic acids or their derivatives (ester compounds or acid anhydride compounds).

[0125] The modified hydrogenated block copolymer is obtained by reacting the aforementioned hydrogenated block copolymer with α,β-unsaturated carboxylic acid or its derivatives in the presence or absence of a free radical initiator, in a molten state, solution state, or slurry state, within a temperature range of 80–350°C. In this case, it is preferable to graft or add α,β-unsaturated carboxylic acid or its derivatives onto the hydrogenated block copolymer in a ratio of 0.01–10% by mass. Furthermore, it can be a mixture of the aforementioned hydrogenated block copolymer and the modified hydrogenated block copolymer in any proportion.

[0126] As for the content of component (c) in this embodiment, when the resin composition of this embodiment is 100% by mass, from the perspective of the impact resistance of the resin composition, the content of component (c) is 2% by mass or more, preferably 5% by mass or more, more preferably 7% by mass or more, and is 30% by mass or less, preferably 25% by mass or less, more preferably 15% by mass or less.

[0127] [(d) Inorganic packing]

[0128] The surface-treated inorganic filler (d) used in this embodiment is not particularly limited (hereinafter also referred to as (d) component), and known components can be used, with fibrous fillers and plate-shaped fillers being preferred.

[0129] Examples of fibrous fillers include, but are not limited to, glass fibers, carbon fibers, whiskers such as potassium titanate whiskers, and calcium silicate (wollastonite).

[0130] Examples of plate-shaped fillers include, but are not limited to, glass flakes, mica, and talc.

[0131] From the perspectives of rigidity and water resistance, glass fiber is the most preferred filler among the above.

[0132] These ingredients can be used alone or in combination of two or more.

[0133] There are no particular limitations on the surface treatment for inorganic fillers. For example, surface treatments using various coupling agents such as silane-based and titanate-based agents can be cited.

[0134] In particular, surface treatment agents containing acidic functional groups are preferred from the perspective of water resistance.

[0135] In addition, from the perspective of improving the adhesion between the resin and the surface-treated inorganic filler, and improving the vibration fatigue characteristics and impact resistance of the resin composition, surface treatment with silane coupling agents such as aminosilane and epoxysilane is preferred.

[0136] The presence of acidic functional groups can be determined by observing whether an acidic peak is detected when the surface treatment agent of the glass fiber is extracted into chloroform and analyzed using Py-GC / MS. Particularly from the perspective of water resistance, glass fibers from which peaks from carboxylic acids can be detected are preferred.

[0137] Regarding acids that constitute compounds containing acid functional groups, examples of unsaturated carboxylic acids or their derivatives include maleic acid, fumaric acid, itaconic acid, acrylic acid, tetrahydrophthalic acid, citraconic acid, crotonic acid, isocrotonic acid, and other unsaturated carboxylic acids. Examples of their derivatives include acid anhydrides, acyl halides, amides, imides, and esters. Specifically, examples include maleic anhydride, acetic anhydride, succinic anhydride, monomethyl maleate, dimethyl maleate, maleimide, and glycidyl maleate.

[0138] The silane coupling agent (silane coupling agent) used in the surface treatment is not particularly limited, but is preferably 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, or 3-epoxypropoxypropyltriethoxysilane.

[0139] As a method for surface treatment of inorganic fillers, for example, when the inorganic filler is glass fiber, an example is to apply an sizing agent and a silane coupling agent together to the surface during the spinning and bundling of the fibrous inorganic filler, followed by drying. When the inorganic filler is in the form of short fibers or powder, an example is to immerse these fillers in a silane coupling agent solution, followed by drying. Here, the drying temperature is preferably 100°C or higher.

[0140] When the inorganic filler is a fibrous filler, it has a fiber length of 2 mm or more when purchased from the inorganic filler manufacturer (before compounding using an extruder).

[0141] When the inorganic filler is fibrous, from the perspective of water resistance, the filler with an average fiber diameter of 20 μm or less is preferred. From the perspective of balancing mechanical properties and dimensional properties, the average fiber diameter is more preferably 5 to 15 μm, and most preferably 12 to 14 μm.

[0142] It should be noted that the average fiber diameter refers to the average fiber diameter of each fibrous filler material measured by observing the fibrous filler material using a scanning electron microscope (SEM), and can be the average of any 10 fibers.

[0143] When the inorganic filler is a plate-shaped filler, from the perspective of fully obtaining the reinforcing effect of the filler, the ratio (R / H) of the average plate diameter (R) to the average thickness (H) of the plate is preferably 5 or more, more preferably 10 or more, and particularly preferably 20 or more.

[0144] As for the content of the component (d) described above, when the resin composition of the present embodiment is taken as 100% by mass, the content of the component (d) is 5% by mass or more, preferably 7% by mass or more, more preferably 10% by mass or more, and less than 50% by mass, preferably 40% by mass or less, more preferably 35% by mass or less, from the aspects of melt flowability, vibration fatigue characteristics, heat resistance, surface appearance of the molded article, and specific gravity of the molded article of the resin composition.

[0145] [Component (e) Hydrotalcite-like Compound]

[0146] As the hydrotalcite-like compound, hydrotalcites described in Japanese Patent Laid-Open No. 60-1241, Japanese Patent Laid-Open No. 9-59475, and the like, for example, hydrotalcite compounds represented by the following formula and the like can be used.

[0147] [M 2+ 1-x M 3+ x (OH)2] x+ [A n- x / n mH2O] x-

[0148] (In the formula, M 2+ represents a divalent metal ion such as Mg 2+ , Mn 2+ , Fe 2+ , Co 2+ and the like, M 3+ represents a trivalent metal ion such as Al 3+ , Fe 3+ , C 3+ and the like. A n- represents an n-valent (particularly monovalent or divalent) anion such as CO3 2- , OH - , HPO4 2- , SO4 2- and the like. x satisfies 0<x<0.5, and m satisfies 0≦m<1.)

[0149] The hydrotalcite-like compound may be a natural product or a synthetic product.

[0150] The hydrotalcite-like compound may be a calcined hydrotalcite obtained by calcination to reduce the amount of OH in its chemical structure.

[0151] In addition, the hydrotalcite-like compound may have been subjected to a surface treatment.

[0152] By adding the hydrotalcite-like compound, the water resistance of the resin composition can be significantly improved.

[0153] It should be noted that hydrotalcite-like compounds can be purchased from Kyowa Chemical Industry Co., Ltd. in the form of "DHT-4A", "DHT-4A-2", "Alcamizer", "KW-2200", etc.

[0154] The hydrotalcite-like compound is preferably uniformly dispersed in the resin. From the perspective of impact resistance, the average particle size of the hydrotalcite-like compound is preferably 1 nm or more and 2 μm or less, more preferably 1 nm or more and 1.5 μm or less, and even more preferably 1 nm or more and 1.0 μm or less.

[0155] It should be noted that the average particle size refers to the average particle size of each hydrotalcite-like compound particle measured by observing the molded sheet using a scanning electron microscope (SEM). The average of the major and minor diameters measured for each particle can be the average value for any 10 particles.

[0156] As for the content of component (e) in this embodiment, assuming the resin composition of this embodiment is 100% by mass, from the perspective of the water resistance and vibration fatigue characteristics of the resin composition, the content of component (e) is 0.01% by mass or more, preferably 0.03% by mass or more, more preferably 0.05% by mass or more, and is 20% by mass or less, preferably 15% by mass or less, more preferably 5% by mass or less.

[0157] [(f) Polyolefins modified with unsaturated carboxylic acids]

[0158] For the purpose of improving the adhesion between the filler and the polypropylene resin forming the matrix, as described later, in addition to the polypropylene resin, a known modified (0.01 to 10 wt% α,β-unsaturated carboxylic acid or its derivative grafted or added to) polyolefin resin obtained by reacting a polyolefin resin with an α,β-unsaturated carboxylic acid or its derivative in the presence or absence of a free radical initiator in a molten or solution state at a temperature of 30 to 350°C can also be used. Furthermore, a mixture of the polypropylene resin and the modified polyolefin resin in any proportion can also be used.

[0159] Examples of polyolefin resins include polypropylene, polyethylene, and ethylene-propylene copolymers. There are no particular limitations as long as the resin contains an olefin in its monomer.

[0160] Examples of α,β-unsaturated carboxylic acids or their derivatives used as modifiers for polyolefin resins include maleic acid, fumaric acid, itaconic acid, acrylic acid, tetrahydrophthalic acid, citraconic acid, crotonic acid, isocrotonic acid, and other unsaturated carboxylic acids. Derivatives include, for example, acid anhydrides, acyl halides, amides, imides, and esters. Specifically, examples include maleic anhydride, monomethyl maleate, dimethyl maleate, maleimide, and glycidyl maleate. Among these, acid anhydrides are preferred, and maleic anhydride is particularly preferred.

[0161] As free radical initiators, they are usually organic or inorganic peroxides, such as tert-butyl peroxide benzoate, tert-butyl hydrogen peroxide, methyl ethyl ketone peroxide, potassium peroxide, hydrogen peroxide, etc.

[0162] (f) The number average molecular weight (Mn) of the polyolefin modified with unsaturated carboxylic acid is preferably 20,000 to 100,000, more preferably 25,000 to 95,000, and even more preferably 30,000 to 95,000.

[0163] It should be noted that the number average molecular weight (Mn) can be determined by gel permeation chromatography (GPC, mobile phase: chloroform, standard substance: polystyrene).

[0164] In this embodiment, if component (d) (inorganic filler) and component (a) (polyphenylene ether resin) can be easily bonded together, the resin composition will exhibit excellent impact resistance and vibration fatigue properties.

[0165] However, the surface adhesion strength of inorganic fillers to resins or other substances is low. Even when inorganic fillers are uniformly mixed in resins, the interfacial strength between inorganic fillers and resins is extremely low. Sometimes, the effect of improving the strength of the composition by adding inorganic fillers cannot be fully obtained.

[0166] To improve the strength enhancement effect, it is preferable to link the resin and inorganic filler using chemical bonds.

[0167] However, the surface of inorganic fillers has extremely low chemical reactivity, so the inorganic fillers themselves may find it difficult to undergo this chemical reaction.

[0168] Therefore, the inorganic filler is surface-treated, and (f) a polyolefin modified with unsaturated carboxylic acid is used. This allows for chemical bonding between the surface of the inorganic filler and the resin via component (f), facilitating the bonding of component (d) (inorganic filler) and component (a) (polyphenylene ether resin). Consequently, the resin composition exhibits excellent impact resistance and vibration fatigue properties.

[0169] Here, inorganic fillers and surface treatment agents are prone to decomposition in the presence of water, which may easily lead to a decrease in strength.

[0170] Here, when the above-mentioned hydrotalcite-like compound is added, or when component (d) containing a compound with acidic functional groups is used in the surface treatment agent, decomposition and property degradation in the presence of water can be suppressed, and excellent impact resistance and vibration fatigue properties can be obtained.

[0171] Especially from the perspectives of strength and cost, glass fiber is preferred as component (d) (inorganic filler). In this case, by subjecting the glass fiber to silane coupling treatment, in which a silane-based compound reacts with the Si-OH groups present on the surface of the glass fiber, chemical bonding between the glass fiber surface and the resin can be achieved with the help of component (f). When using glass fiber, there is a problem that the products of the condensation reaction based on Si-OH groups and silane-based compounds are prone to decomposition in the presence of water. As mentioned above, this problem can be solved by adding a hydrotalcite-like compound or by adding component (d), which contains a compound with acidic functional groups in the surface treatment agent.

[0172] As for the content of component (f) in this embodiment, assuming the resin composition of this embodiment is 100% by mass, from the perspective of the impact resistance and vibration fatigue characteristics of the resin composition, the content of component (f) is 0.1% by mass or more, preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and is 20% by mass or less, preferably 15% by mass or less, more preferably 10% by mass or less.

[0173] [Phosphorus compounds]

[0174] In this embodiment, the resin composition may contain phosphorus compounds.

[0175] Examples of phosphorus compounds include organophosphorus compounds, red phosphorus, and inorganic phosphates.

[0176] As for organophosphorus compounds, there is no particular limitation as long as they are phosphorus compounds having organic substituents (in this embodiment, groups having PC bonds and POC bonds are included). Examples include esters of phosphoric acid (also referred to as "phosphate esters" below), esters of phosphorous acid (also referred to as "phosphite esters" below), and phosphonite esters.

[0177] More specifically, examples of phosphate esters include trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, tricyclohexyl phosphate, triphenyl phosphate, tricresyl phosphate, tri(xylene) phosphate, toluene diphenyl phosphate, xylene phosphate, dimethyl ethyl phosphate, methyl dibutyl phosphate, ethyl dipropyl phosphate, and hydroxyphenyl diphenyl phosphate, all of which are used as flame retardants. These substances are also modified phosphate ester compounds with various substituents, and various condensation-type condensed phosphate ester compounds.

[0178] Examples of phosphites include trinonylphenyl phosphite, triphenyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol-diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol-diphosphite, and 3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosspiro[5,5]undecane, which are also used as phosphorus-based antioxidants.

[0179] Examples of phosphonites include tetra(2,4-di-tert-butylphenyl)4,4'-biphenyl diphosphonite and tetra(2,4-di-tert-butyl-5-methylphenyl)4,4'-biphenyl diphosphonite.

[0180] In this embodiment, from the perspective of water resistance and vibration fatigue characteristics, when the resin composition is 100% by mass, the phosphorus element contained in the resin composition is preferably 0.3% by mass or less, more preferably 0.2% by mass or less, and particularly preferably 0.1% by mass or less.

[0181] As a method for determining the phosphorus content in the resin composition, the following method can be cited as an example. In a clean room, 0.25 g of a pre-dried thermoplastic resin composition is accurately weighed into a fluoropolymer container. Sulfuric acid and nitric acid are added, and the composition is subjected to pressurized acid decomposition using a microwave decomposition apparatus to obtain a decomposition solution. 25 mL of this decomposition solution is weighed as the test solution, and the test solution is analyzed using an ICP mass spectrometer (with cobalt as an internal standard) via an absolute calibration curve method. More specifically, the determination can be performed using the method described in the examples below.

[0182] [Coloring agent]

[0183] In this embodiment, there are no particular limitations on the coloring method of the resin composition, and one or more colorants selected from known organic dyes / pigments and inorganic pigments can be used.

[0184] Examples of organic dyes / pigments include azo lake pigments, benzimidazolone pigments, diaryl compound pigments, fused azo pigments, phthalocyanine pigments such as phthalocyanine blue and phthalocyanine green, isoindolineone pigments, quinolineone pigments, quinacridone pigments, perylene pigments, anthraquinone pigments, violet ketone pigments, dioxazine violet, fused polycyclic pigments such as azazine pigments, and carbon black.

[0185] Among them, the preferred carbon black is dibutyl phthalate (DBP) with an absorption capacity of less than 250 mL / 100 g, more preferably less than 150 mL / 100 g, and a nitrogen adsorption specific surface area of ​​less than 900 m². 2 / g, further preferred to be less than 400m 2 / g. When these parameters are within this range, compositions with particularly excellent colorability, mechanical strength, and flame retardancy can be obtained. The DBP absorbance and nitrogen adsorption specific surface area mentioned here refer to values ​​obtained by measurement using the methods specified in ASTM D2414 and JIS K6217, respectively.

[0186] Examples of azazon dyes include Solvent Black 5 (CI50415, CAS No. 11099-03-9), Solvent Black 7 (CI50415:1, CAS No. 8005-20-5 / 101357-15-7), and Acid Black 2 (CI50420, CAS No. 8005-03-6 / 68510-98-5) in terms of color index.

[0187] Examples of inorganic pigments include metal oxides other than iron oxide, such as titanium oxide, zinc oxide, and chromium oxide, as well as composite metal oxides such as titanium yellow, cobalt blue, and ultramarine.

[0188] Regarding the preferred amounts of the aforementioned colorants, when the total resin composition is 100% by mass, the amounts are: carbon black 2% by mass or less, azazine dyes 2% by mass or less, and inorganic pigments 8% by mass or less. More preferably, the amounts are: carbon black 1% by mass or less, azazine dyes 1% by mass or less, and inorganic pigments 5% by mass or less.

[0189] By adding the above-mentioned amount, a good balance between impact resistance and mechanical properties can be maintained. Furthermore, in applications requiring flame retardancy, the above-mentioned amount is preferred from a flame retardancy perspective.

[0190] [Other Additives]

[0191] In this embodiment, in addition to the above-mentioned components, other inorganic filler materials and additives may be added at any stage as needed, within the range that does not impair the effect of this embodiment.

[0192] Examples of additive components include other thermoplastic resins such as polyester and polyolefins, plasticizers (low molecular weight polyolefins, polyethylene glycol, fatty acid esters, etc.), as well as antistatic agents, nucleating agents, flow improvers, reinforcing agents, various peroxides, spreading agents, copper-based heat stabilizers, organic heat stabilizers represented by hindered phenolic antioxidants, antioxidants, ultraviolet absorbers, light stabilizers, etc.

[0193] When the total amount of the resin composition is 100% by mass, the preferred amounts of these components are 15% by mass or less, more preferably 13% by mass or less, and even more preferably 10% by mass or less.

[0194] [Morphology of the resin composition]

[0195] As for the form (dispersion form) of the resin composition in this embodiment, from the perspective of exhibiting chemical resistance, it is preferable that component phase (b) is the matrix phase and component phase (a) is the dispersed phase, and more preferably that component phase (b) is the matrix phase and component phase (a) is the dispersed phase.

[0196] (a) Component phase contains component (a), for example, it can be composed of a component containing component (a) and component (c), or it can be composed of a component containing component (a), component (c) and component (d), or it can be composed of component (a).

[0197] (b) The component phase contains component (b), and can be composed of components containing components (b) and (d), or components containing components (b), (d) and (e), or can be composed of component (b).

[0198] It should be noted that the morphology of the resin composition can be observed using a transmission electron microscope (TEM) or similar instruments.

[0199] In particular, component phase (a) is preferably dispersed with an average minor axis diameter of 2 μm or less. Furthermore, from the perspective of impact resistance, component phase (a) is more preferably dispersed with an average minor axis diameter of 10 nm or more but less than 1 μm.

[0200] In addition, it is preferable to disperse the material in a manner where the average major axis diameter / average minor axis diameter is 1 to 10.

[0201] It should be noted that the average minor axis diameter and average major axis diameter can be determined by observation using a transmission electron microscope (TEM).

[0202] By making component (c) not only contained in component (a) phase, but also surrounded by component (c) phase, component (a) contained in component (a) phase can become a more thermally stable dispersion state, which is preferred from the perspective of impact resistance.

[0203] Furthermore, from the perspective of impact resistance, it is preferable that in at least 10 of the 100 phases containing component (a), the linear phase containing component (c) with a length of 75 nm or more is dispersed in a state where it is located inside the phase containing component (a). The reason for improving impact resistance through such a dispersion state is not yet certain, but it is presumed that by forming a morphology in which component (c) with excellent impact resistance is contained within a phase of component (a) with poor impact resistance, the impact resistance of the resin composition can be improved.

[0204] The linear phase containing component (c) with a length of 75 nm or more located inside the phase containing component (a) refers to a linear phase that is stained darker than component (a) in a TEM image observed by staining components (b) and (c) with ruthenium tetroxide. This phase exists within the phase containing component (a) and is located outside the interface between the phase containing component (a) and the phase containing component (b).

[0205] At this point, regarding the case where component (b) is contained in the dispersed phase, since the dispersed phases are fused together, there is a possibility that the coloring is relatively darker than that of component (a). Therefore, it is considered that this case should be excluded from "a linear phase containing component (c) with a length of more than 75 nm that is inside the phase containing component (a)".

[0206] Furthermore, at this point, all phases containing component (c) that do not exist at the interface between the phase containing component (a) and the phase containing component (b) are included in the above scope. Even if the phase containing component (c) is connected to a phase containing component (c) that exists at the interface between the phase containing component (a) and the phase containing component (b), it is still a phase containing component (c) that is in the phase containing component (a).

[0207] When determining the length of a linear phase containing component (c), the phase containing component (c) present at the interface between the phase containing component (a) and the phase containing component (b) is excluded, and the length of the phase containing component (c) extending away from the interface is taken as the length of the phase containing component (c) within the phase containing component (a).

[0208] A linear phase containing component (c) can be formed in a curved or branched manner, or it can be drawn in an arc, and it can be divided into two or more strands, or it can be repeatedly connected. In this case, the total length of the phase containing component (c) that extends off the interface in a phase containing component (a) is taken as the length of the phase containing component (c) in the phase containing component (a).

[0209] As a specific example, the state of at least 10 of the 100 phases containing component (a) and containing component (c) in the form of linear structures with a length of 75 nm or more is shown. Figure 1 It should be noted that, Figure 1 This is an image of the resin composition of Example 2 described later.

[0210] Here, Figure 1 The image is obtained by staining components (b) and (c) with ruthenium tetroxide on a linear phase containing component (a) inside the phase containing component (a) and observing it with TEM. Figure 1 In the diagram, the parts dyed light gray are phases containing component (a), the lightest parts are phases containing component (b), and the parts dyed dark gray or black are phases containing component (c).

[0211] From the perspective of impact resistance, the length of the linear phase containing component (c) is preferably 75 nm or more.

[0212] Furthermore, the width of the linear phase containing component (c) located inside the phase containing component (a) is preferably 1 to 1000 nm, more preferably 1 to 500 nm, from the viewpoint of obtaining more superior vibration fatigue characteristics.

[0213] The above values ​​are the average values ​​obtained by observing the linear (c) components present in any 100 (a) component dispersed phases in an image obtained by TEM observation of any cross section of the resin composition.

[0214] As methods for controlling the morphology as described above, examples include: adjusting the vinyl content, structure, and molecular weight of component (c); appropriately adjusting the molecular weight of component (a); adjusting the mixing ratio of polyphenylene ether resin (a) and polypropylene resin (b); and feeding polypropylene resin (b) into the extruder in batches from two or more feed ports; etc. Among these, adjusting the vinyl content and molecular weight of component (c) is the most effective.

[0215] For example, more specifically, increasing the vinyl content of component (c) tends to result in a suitable morphology; if the vinyl content of component (c) is too high, adjustments to the amount added may be necessary. If the proportion of component (a) relative to the total of polyphenylene ether resin (a) and polypropylene resin (b) is excessively increased, component (a) becomes the matrix, tending to result in an undesirable morphology.

[0216] Next, the conditions for obtaining the morphological image and the image processing method for the obtained image will be explained.

[0217] After preparing ultrathin sections using an ultramicrotome, the slides obtained by staining components (b) and (c) with ruthenium tetroxide were photographed using a transmission electron microscope (trade name "HT7700", manufactured by Hitachi High Technology Co., Ltd.) set to a magnification of 10,000x and an accelerating voltage of 100.0 kV. Fields of view were selected from the obtained images to include more than 100 components (a) of the dispersed phase.

[0218] Next, the obtained morphological image (printed paper) was acquired using a scanner (device: RIKOH MPC5503, conditions: full-color printed paper photograph, resolution 300 dpi) and digitized. Image Pro10 was used for image analysis; the digitized image was loaded into Image Pro10 and binarized under Auto conditions, performing a two-grayscale conversion (white / black). As described above, relative to the white to gray (a) polyphenylene ether resin and (b) polypropylene resin, (c) mixture is relatively black, and therefore can be identified.

[0219] Based on the obtained binarized image, arbitrarily select 100 phases (dispersed phases) containing component (a), measure the average major axis diameter and average minor axis diameter of the phases containing component (a), and measure the length and width of the phase containing component (c) located inside the phase containing component (a).

[0220] In this embodiment, the value obtained by averaging the results of the above measurements is used as the result.

[0221] In addition, the morphological image may sometimes reflect defects that occur at the measurement section (damage caused during section making by ultrathin slicers, voids existing in the resin, etc.). The image range for binarization is selected in a way that does not include such parts.

[0222] The melt flow rate of the resin composition in this embodiment is preferably 1 to 20 g / 10 min, more preferably 2 to 20 g / 10 min, and even more preferably 3 to 20 g / 10 min.

[0223] It should be noted that the melt mass flow rate refers to the value measured according to ISO 1133 at 250°C and a load of 10.0 kg.

[0224] [Method for manufacturing the resin composition]

[0225] The resin composition of this embodiment can be manufactured by melt-blending the above-mentioned components (a) to (e), component (f) if necessary, and other components.

[0226] The method for manufacturing the resin composition of this embodiment is not particularly limited as long as it allows for the melt mixing of components (a) to (e), component (f) if necessary, and other components.

[0227] A suitable method for manufacturing the resin composition of this embodiment includes the following steps: Step (1-1) involves melting and mixing the total amount of component (a) and all or part of components (b) and (c) to obtain a compound; Step (1-2) involves adding the balance of components (b) and (c) to the compound obtained from step (1-1) (except where all of components (b) and (c) were used in step (1-1)), and further melt-blending to obtain the compound; and Step (1-3) involves adding the total amount of component (d) to the compound obtained in step (1-2) and further performing melt mixing.

[0228] The addition of component (e) can be any of steps (1-1), (1-2), or (1-3), and can be done individually or in batches. The same applies to component (f).

[0229] A suitable manufacturing method for the resin composition of this embodiment can be a multi-stage melt-blending method. It should be noted that there is no particular limitation as long as the multi-stage process involves two or more stages.

[0230] The method in this embodiment includes, for example, the following steps: In stage 1, the total amount of component (a), a portion of component (b), the total amount of component (c), and the total amount of component (e) are melt-blended to obtain granules; and In the second stage, the granules obtained in the first stage, the balance of component (b), and component (d), and component (f) if necessary, are added to further carry out the melt-blending process.

[0231] In this case, the total amount of component (b) can be added in stage 2.

[0232] Furthermore, as a suitable manufacturing method for the resin composition of this embodiment, the following masterbatch method can be cited: a resin composition (masterbatch) containing specific components at a high concentration is prepared in advance, and then the masterbatch is diluted to obtain a resin composition containing each component at a desired concentration.

[0233] In this embodiment, the method includes, for example, the following steps: In stage 1, the total amount of component (a), a portion of component (b), the total amount of component (c), and the total amount of component (d) are melt-blended to obtain masterbatch pellets containing component (d) at a higher concentration than that in the final composition; and In the second stage, the masterbatch granules and the balance of component (b), and component (f) if necessary, are added, and further melt-blended to obtain the final composition.

[0234] In this case, the total amount of component (b) can be added in stage 2.

[0235] There are no particular limitations on the melt mixing mill suitable for performing the melt mixing of the various components in the above-described manufacturing method. Examples include multi-screw extruders such as single-screw extruders and twin-screw extruders, as well as heated melt mixing mills such as rollers, kneaders, Brayburn plasticizers, and Banbury mixers. In particular, from the perspective of mixability, twin-screw extruders are preferred. Specifically, examples of twin-screw extruders include the ZSK series manufactured by Coperion, the TEM series manufactured by TOSHIBAMACHINE CO.,LTD, and the TEX series manufactured by Nippon Steel Works.

[0236] The following describes suitable implementation methods when using extruders such as single-screw extruders, twin-screw extruders, and other multi-screw extruders.

[0237] There are no particular restrictions on the type and specifications of extruders; they can be any well-known type and specification.

[0238] The L / D (effective barrel length / barrel inner diameter) of the extruder is preferably 20 or more, more preferably 30 or more, and preferably 75 or less, more preferably 60 or less.

[0239] Regarding the configuration of the extruder, it may have two or more different raw material supply ports, two or more vacuum exhaust ports, and one or more liquid filling pumps (described later). In addition, regarding the configuration of these devices, from the perspective of impact resistance, it is more preferable to have a first raw material supply port upstream in the direction of raw material flow, a first vacuum exhaust port downstream of the first raw material supply port, a second raw material supply port downstream of the first vacuum exhaust port, a liquid filling pump downstream of the second raw material supply port, and a second vacuum exhaust port downstream of the liquid filling pump.

[0240] Furthermore, there is no particular limitation on the method of supplying raw materials at the second raw material supply port. It can be a simple method of adding materials from the upper opening of the raw material supply port, or a method of adding materials from the side opening using a forced side feeder. In particular, from the perspective of stable supply, the method of adding materials from the side opening using a forced side feeder is preferred.

[0241] When the components are melt-blended, the melting temperature is usually 270–320°C.

[0242] In particular, from the perspective of the fuming properties and chemical resistance of the resin composition, it is preferable that the melt mixing temperature is between 300°C and 320°C between the first and second raw material supply ports.

[0243] Here, from the perspective of the chemical resistance exhibited by the fuming property of the resin composition, it is preferable to change the set temperature between the first raw material supply port and the second raw material supply port, and in the downstream portion of the second raw material supply port. Specifically, it is preferable to set the set temperature between the first raw material supply port and the second raw material supply port to be 300°C or more and 320°C or less, and to set the set temperature in the downstream portion of the second raw material supply port to be 270°C or more and less than 300°C.

[0244] There is no particular limit to the screw speed, which is usually between 100 and 1200 rpm.

[0245] [Molded body]

[0246] The molded body of this embodiment is composed of the resin composition of this embodiment described above.

[0247] The molded body of the resin composition in this embodiment is not particularly limited, and examples include automotive parts, interior and exterior parts of electrical equipment, and other parts. Automotive parts are not particularly limited, and examples include exterior parts such as bumpers, mudguards, door panels, various trim strips, logos, engine hoods, wheel covers, roof panels, spoilers, and various aerodynamic kits; interior parts such as instrument panels, control boxes, and trim panels; secondary battery pack components for automobiles, electric vehicles, and hybrid electric vehicles; and lithium-ion secondary battery components. Similarly, interior and exterior parts of electrical equipment are not particularly limited, and examples include housings and chassis of various computers and peripherals, other OA equipment, televisions, video recorders, and various CD players; components used in refrigerators, air conditioners, and LCD projectors. Other parts include wires / cables obtained by coating metal conductors or optical fibers; fuel cells for solid methanol batteries; fuel cell water pipes; water-cooling tanks; boiler housings; ink peripheral components or parts for inkjet printers; furniture (chairs, etc.); chassis; water pipes; and connectors.

[0248] [Manufacturing method of molded body]

[0249] The molded body of this embodiment can be manufactured by molding the resin composition of this embodiment described above.

[0250] The manufacturing method of the molded body in this embodiment is not particularly limited. Examples include injection molding, extrusion molding, extrusion molding, blow molding, compression molding, etc. However, from the perspective of more effectively obtaining the effects of this embodiment, injection molding is preferred.

[0251] Example

[0252] The following examples illustrate this implementation method, but this implementation method is not limited to these examples.

[0253] The raw materials used in the resin compositions and molded articles of the examples and comparative examples are shown below.

[0254] (a) Polyphenylene ether resin

[0255] (a-1) Polyphenylene ether resin obtained by oxidative polymerization of 2,6-xylenol

[0256] The specific viscosity of this polyphenylene ether resin (0.5 g / dL, chloroform solution, measured at 30°C) is 0.52 dL / g.

[0257] (a-2) Polyphenylene ether resin obtained by oxidative polymerization of 2,6-xylenol.

[0258] The specific viscosity of this polyphenylene ether resin (0.5 g / dL, chloroform solution, measured at 30°C) is 0.40 dL / g.

[0259] (a-3) Polyphenylene ether resin obtained by oxidative polymerization of 2,6-xylenol

[0260] The specific viscosity of this polyphenylene ether resin (0.5 g / dL, chloroform solution, 30℃) is 0.32 dL / g.

[0261] (b) Polypropylene

[0262] (b-1) Polypropylene homopolymer with an MFR of 15 g / 10 min

[0263] (b-2) MFR=2g / 10min polypropylene homopolymer

[0264] (b-3) Polypropylene homopolymer with an MFR of 0.4 g / 10 min

[0265] It should be noted that the MFR was measured according to ISO 1133 under conditions of 230°C and 2.16 kg load.

[0266] (c) Mixture

[0267] (c-1)

[0268] A block copolymer with a II-I-II-I block structure (where polymer block I is composed of polystyrene and polymer block II is composed of polybutadiene) was synthesized using a known method. The block copolymer synthesized using the known method was then hydrogenated. No polymer modification was performed. The properties of the resulting unmodified hydrogenated block copolymer are shown below.

[0269] Polystyrene content in the hydrogenated block copolymer: 44% by mass; Number average molecular weight (Mn): 95,300; Weight average molecular weight (Mw): 113,600; 1,2-vinyl bound content (total vinyl bound content) in the hydrogenated polybutadiene blocks: 79%; Hydrogenation rate of the polybutadiene portion constituting the polybutadiene blocks: 99%.

[0270] (c-2)

[0271] A block copolymer with a II-I-II-I block structure (where polymer block I is composed of polystyrene and polymer block II is composed of polybutadiene) was synthesized using a known method. The block copolymer synthesized using the known method was then hydrogenated. No polymer modification was performed. The properties of the resulting unmodified hydrogenated block copolymer are shown below.

[0272] Polystyrene content in the hydrogenated block copolymer: 66% by mass; Number average molecular weight (Mn) of the hydrogenated block copolymer: 57,000; Weight average molecular weight (Mw): 60,400; 1,2-vinyl bound content (total vinyl bound content) in the hydrogenated polybutadiene blocks: 41%; Hydrogenation rate of the polybutadiene portion constituting the polybutadiene blocks: 99%.

[0273] (d) Inorganic packing

[0274] (d-1) Components of glass fibers with an average fiber diameter of 13 μm that have been surface-treated with a surface treatment agent containing acid functional groups. The presence of acid functional groups in the surface treatment agent was confirmed by determination using Py-GC / MS.

[0275] (d-2) Glass fibers with an average fiber diameter of 13 μm.

[0276] (d-3) Glass fibers with an average fiber diameter of 10.5 μm.

[0277] (e) Type of hydrotalcite compounds

[0278] (e-1) Kyowa Chemical Industry manufactures DHT-4C hydrotalcite, Mg 4.5 Al2(OH) 13 CO3·3.5H2O (representative structure), surface treated with higher fatty acids, average particle size 0.40μm.

[0279] (e-2) Kyowa Chemical Industry manufactures KW2200 calcination process for hydrotalcite and Mg 0.7 Al 0.3 O 1.15 (Representative structure), average particle size 0.45 μm.

[0280] (f) Polyolefins modified with unsaturated carboxylic acids

[0281] (f-1) Polypropylene modified with maleic anhydride with a number-average molecular weight (Mn): 60,000 and a weight-average molecular weight (Mw): 91,000.

[0282] (f-2) Polyethylene propylene modified with maleic anhydride with a number-average molecular weight (Mn): 32,000 and a weight-average molecular weight (Mw): 83,000.

[0283] (Other ingredients) Organophosphorus compounds

[0284] Bisphenol A condensed phosphate ester: Manufactured by Daihachi Chemical Co., Ltd., trade name "CR-741", the main component is the component with n=1 in the following chemical formula (based on the area ratio of liquid chromatography analysis of approximately 85%, acid value = 0.01 KOH mg / g).

[0285] [Chemistry 1]

[0286] The melt mixer used in the manufacture of the resin compositions of the various embodiments and comparative examples was a twin-screw extruder (Coperion, ZSK-25). The extruder had an L / D ratio of 35.

[0287] 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 it, and a vacuum exhaust port is provided downstream of it. Regarding the method of supplying raw material to the second supply port, a side feeder is used to supply it from the extruder side opening. Using the extruder configured as described above, the following components are mixed according to the composition shown in Table 1: (a) polyphenylene ether resin, (b) polypropylene, (c) additives, (d) surface-treated inorganic filler, (e) hydrotalcite-like compound, and (f) polyolefin modified with unsaturated carboxylic acid. The mixture is melt-blended at an extrusion temperature of 270–320°C, a screw speed of 300 rpm, and an output of 20 kg / h to obtain a composition in granular form.

[0288] In addition, the resin granules obtained above were fed into a small injection molding machine (trade name: IS-100GN, manufactured by TOSHIBA MACHINE) set to 240–280°C, and evaluation test pieces for the tests described later were produced under a mold temperature of 60°C. JIS K7139 type A1 test pieces were prepared and subjected to heat history treatment by standing in a gear oven at 80°C for 24 hours. These test pieces were used as specimens for impact resistance / water resistance testing and morphological observation.

[0289] In addition, for the purpose of evaluating vibration fatigue characteristics, a No. III test piece is prepared according to the cantilever bending test method of JIS-7119.

[0290] (1) Morphology

[0291] Ultrathin sections with a thickness of 80 nm were prepared from the obtained morphological observation samples using an ultramicrotome. The sections were stained with ruthenium tetroxide and observed at 10,000x magnification using a TEM (Hitachi High-Technologies HT7700).

[0292] Using the above method, the length of the phase containing component (c) in the phase containing component (a) is determined by observing the image. Among 10 or more of the 100 phases containing component (a), the case where the linear phase containing component (c) with a length of 75 nm or more is located inside the phase containing component (a) is marked as "○", and the case where it is not the case is marked as "×".

[0293] In addition, the average minor axis diameter of the phase containing component (a) is determined from the observed image using the same method described above. Cases with an average minor axis diameter of 10 nm or more but less than 1 μm are marked as "○", and cases that are not in this case are marked as "×".

[0294] (2) Phosphorus content

[0295] The surface of the obtained resin composition granules was cleaned with pure water in a clean room. 0.25 g was then weighed as a sample. This sample was placed in a Teflon (registered trademark) decomposition container, and sulfuric acid and nitric acid were added. Pressure acid decomposition was performed using a microwave decomposition device. 25 mL of the decomposition solution was then measured as the assay solution. The assay solution was analyzed using an ICP mass spectrometer (internal standard: cobalt) using the absolute calibration curve method to determine the phosphorus content (mass %).

[0296] (3) Impact resistance

[0297] The impact / water resistance test specimen prepared by the above molding process is cut to produce a test piece for the Chevron impact strength test. No notch is cut at this stage.

[0298] For the test piece used for the above-mentioned chevron impact strength test, the chevron impact strength (kJ / m²) of the test piece was determined according to JIS K7111-1 / 1eA. 2 ).

[0299] As an evaluation benchmark, the higher the measured value, the better the impact resistance is judged.

[0300] (4) Melt mass flow rate

[0301] The melt flow rate (g / 10 min) of the obtained resin composition granules was evaluated according to ISO 1133 at 250 °C and a load of 10.0 kg.

[0302] As an evaluation benchmark, the larger the measured value, the better the fluidity is judged.

[0303] (5) Water resistance

[0304] Using the aforementioned test piece for cherubic impact strength testing, the specimen was kept under constant temperature and humidity conditions of 23 degrees Celsius and 50% for 24 hours. Then, according to JIS K7111-1 / 1eU, the cherubic impact strength (kJ / m²) of the test piece was measured without any notches. 2 The obtained value is taken as A(kJ / m). 2 ).

[0305] In addition, the test piece was placed in a high-pressure steam testing machine (ESPEC TPC-221) at 130 degrees Celsius and 100% humidity for 350 hours. Afterward, it was removed and kept under constant temperature and humidity conditions of 23 degrees Celsius and 50% humidity for 24 hours. Then, according to JIS K7111-1 / 1eU, the Chiebelle impact strength (kJ / m²) of the unnotched test piece was determined. 2 The value obtained is taken as B (kJ / m³). 2 ).

[0306] Here, as an indicator of water resistance, the property retention rate C (%) after being placed in the high-pressure cooking test chamber is calculated using the following formula.

[0307] C = (A / B) × 100

[0308] As an evaluation benchmark, the higher the measured value, the better the water resistance is judged.

[0309] (6) Vibration fatigue characteristics

[0310] Based on the JIS-7119 cantilever bending test piece No. III manufactured using the above molding process, the number of vibrations at fracture was determined using a bending fatigue testing machine (trade name: B70-TH, manufactured by Toyo Seiki Co., Ltd.) under the conditions of temperature: 90°C, frequency: 30Hz, and load: 20MPa, according to JIS-7119. Measurements were performed with n=4, and the average values ​​are shown. If the test did not fracture after more than 1,000,000 vibrations, the test was interrupted, and this is recorded as "not fractured" in the table of examples.

[0311] As an evaluation criterion, the more vibration cycles before fracture, the better the vibration fatigue resistance.

[0312] (Examples 1-25, Comparative Examples 1-23)

[0313] For each embodiment and each comparative example, physical property tests were conducted using the above-described measurement methods (1) to (5).

[0314] The results are shown in Tables 1 and 2.

[0315] [Table 1-1]

[0316] [Table 1-2]

[0317] [Table 2-1]

[0318] [Table 2-2]

[0319] Industrial applicability

[0320] According to the present invention, a polypropylene / polyphenylene ether resin composition with excellent water resistance can be obtained even when inorganic fillers are added.

Claims

1. A resin composition comprising (a) a polyphenylene ether resin, (b) a polypropylene resin, (c) an additive, (d) an inorganic filler, (e) a hydrotalcite-like compound, and (f) a polyolefin modified with an unsaturated carboxylic acid. The mixture (c) is selected from one or more of the following groups: hydrogenated block copolymer, which is formed by hydrogenating at least a portion of 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; copolymer having a polystyrene block chain-polyolefin block chain; and copolymer having a polyphenylene ether block chain-polyolefin block chain. The inorganic filler (d) comprises an inorganic filler that has been surface-treated using a surface treatment agent containing acid functional groups.

2. The resin composition according to claim 1, wherein, The unnotched impact strength is 10 kJ / m 2 above.

3. The resin composition according to claim 1 or 2, wherein, The inorganic filler (d) comprises glass fiber.

4. The resin composition according to any one of claims 1 to 3, wherein, The inorganic filler (d) comprises fibrous fillers with a fiber diameter of 11 μm to 20 μm.

5. The resin composition according to any one of claims 1 to 4, wherein, The particle size of the (e) type hydrotalcite compound is greater than 1 nm and less than 2 μm.

6. The resin composition according to any one of claims 1 to 5, wherein, The specific viscosity of the polyphenylene ether resin (a) is 0.35 dL / g or higher.

7. The resin composition according to any one of claims 1 to 6, wherein, The hydrogenation rate of the mixture in (c) is above 90%.

8. The resin composition according to any one of claims 1 to 7, wherein, The vinyl binding content of the mixture in (c) is greater than 50%.

9. The resin composition according to any one of claims 1 to 8, wherein, The phosphorus content is less than 0.3% by mass.

10. The resin composition according to any one of claims 1 to 9, wherein, The phase comprising (a) the polyphenylene ether resin forms a dispersed phase, and the phase comprising (b) the polypropylene resin forms a matrix phase.

11. The resin composition of claim 10, wherein, The phase comprising the polyphenylene ether resin of (a) has an average short axis diameter of 10 nm or more and 1 μm or less.

12. The resin composition of claim 10 or claim 11, wherein, In 10 or more of the 100 phases containing the polyphenylene ether resin of (a), a linear phase containing the mixture of (c) with a length of 75 nm or more is located inside the phase containing the polyphenylene ether resin of (a).

13. A molded article formed from the resin composition of any one of claims 1 to 12.

14. The molded article as claimed in claim 13, wherein it is an electrical / electronic component for automotive use or a water-using component.

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