JP5088647B2 - Resin composition and process for producing the same - Google Patents

Description

  The present invention relates to a resin composition excellent in oil resistance, chemical resistance, heat resistance, rigidity, and molding processability that can be used in the electric / electronic field, automobile field, and other various industrial material fields. The present invention relates to a resin composition having an improved molding cycle and a method for producing the same.

  Polyphenylene ether resins are known as engineering plastics with excellent flame retardancy, heat resistance, dimensional stability, non-water absorption and electrical properties, but they have poor melt flowability and inferior moldability, There are drawbacks in that it is poor in solvent resistance and impact resistance. Polyolefin resins, on the other hand, are low specific gravity and inexpensive plastics, and are excellent in chemical resistance, solvent resistance, molding processability, etc., so they are used in various fields such as automotive parts, electrical / electronic equipment parts, and household electrical appliances. ing. Therefore, it is predicted that a resin composition excellent in moldability, heat resistance, and flame retardancy can be obtained by mixing these two resins, making up for each other's shortcomings, and drawing out the strengths. Resin material can be expected.

  For this reason, many proposals have been made regarding this polyolefin / polyphenylene ether polymer alloy. For example, a proposal has been made to improve solvent resistance and impact resistance by blending polyphenylene ether with polyolefin (for example, see Patent Document 1). In addition, there is a description on improvement of impact resistance and solvent resistance by blending polyphenylene ether or polyphenylene ether and styrene resin with a hydrogenated block copolymer (for example, see Patent Document 2). Polyphenylene ether or polyphenylene ether And impact resistance and solvent resistance by blending a styrene-based resin with a polyolefin / hydrogenated block copolymer = 20-80 parts by weight / 80-20 parts by weight of a premix and a hydrogenated block copolymer (For example, refer to Patent Document 3).

Furthermore, improvement of impact resistance by blending polyphenylene ether with hydrogenated block copolymer and polyolefin is described (for example, see Patent Documents 4 to 5). And it is described that impact resistance is improved by blending polyphenylene ether with polyolefin and hydrogenated block copolymer (see, for example, Patent Documents 6 to 7).
In addition, a resin composition excellent in chemical resistance and processability has been proposed by blending a specific hydrogenated block copolymer for modification of a resin composition comprising a polyolefin resin and a polyphenylene ether resin (for example, a patent) Reference 8-13).
Further, the present applicant has proposed a resin composition having excellent compatibility, rigidity and heat resistance, and excellent solvent resistance, comprising polyphenylene ether, polyolefin and a specific hydrogenated block copolymer (for example, Patent Document 14). To 21).

  Furthermore, a method for producing a resin composition comprising a polyphenylene ether and a polyolefin and a hydrogenated block copolymer or a rubbery polymer and having an excellent balance between mechanical properties, particularly impact strength and rigidity has been proposed (for example, (See Patent Documents 22 to 23). Also, a method for producing a resin composition having good compatibility between a polyphenylene ether resin and a polyolefin and having excellent mechanical properties, particularly impact resistance has been proposed (see, for example, Patent Document 24). In response to demands for higher heat resistance and dimensional accuracy, it has been proposed to add at least one fibrous, plate-like, and granular inorganic filler (see, for example, Patent Documents 25 to 27).

US Pat. No. 3,361,851 US Pat. No. 3,994,856 U.S. Pat. No. 4,145,377 U.S. Pat. No. 4,166,055 U.S. Pat. No. 4,239,673 U.S. Pat. No. 4,383,082 European Published Patent No. 115712 JP-A-63-113058 JP-A-63-225642 US Pat. No. 4,863,997 Japanese Unexamined Patent Publication No. 3-72512 JP-A-4-183748 Japanese Patent Laid-Open No. 5-320471 JP-A-2-225563 Japanese Patent Laid-Open No. 3-185058 Japanese Patent Laid-Open No. 5-70679 JP-A-5-295184 JP-A-6-9828 JP-A-6-16924 JP-A-6-57130 JP-A-6-136202 JP-A-4-28739 JP-A-4-28740 JP-A-7-166026 JP-A-7-90183 JP 2000-119454 A JP 2005-105037 A

  In the above prior art, Patent Document 26 and Patent Document 27 include a resin composition substantially composed of polyphenylene ether or polyphenylene ether and an aromatic vinyl compound polymer, and an olefin resin and a hydrogenated block copolymer or rubber-like resin. A thermoplastic resin composition containing a polymer and an inorganic filler has been proposed. However, in the case of a polypropylene resin composition, the molded product is likely to be warped and deformed, and there is a disadvantage that the molding cycle becomes longer because it is necessary to lengthen the mold cooling time to suppress the warpage. . In the above thermoplastic resin composition, when the content of the polyolefin resin contained in the composition increases, the improvement effect is not necessarily sufficient. An object of the present invention is to provide a resin composition that is excellent in warping, molding cycle, rigidity, heat resistance, and water vapor permeability resistance of a molded article that could not be improved by the above-described thermoplastic resin compositions proposed previously. It is in.

  In view of the current situation, the present inventors have a high level of resin composition comprising a polypropylene-based resin and a polyphenylene ether-based resin, a hydrogenated block copolymer as an admixture, and fibrous and plate-like inorganic fillers. In order to give rigidity and heat resistance, the conventional technology has been studied by combining specific fibrous and plate-like inorganic fillers and specifying the weight ratio of the fibrous and plate-like inorganic fillers used. Thus, it was found that a resin composition excellent in warpage, molding cycle, rigidity, heat resistance and water vapor permeability could be obtained, and the present invention was achieved.

That is, this invention relates to the resin composition described below, its manufacturing method, and a container using the same.
[1] (a) Crystalline propylene homopolymer and maleic anhydride modified polypropylene forming a matrix phase , or 45 to 95 parts by weight of crystalline propylene-ethylene block copolymer resin and maleic anhydride modified polypropylene, (b) (C) at least one polymer mainly composed of a vinyl aromatic compound, based on 55 to 5 parts by weight of the polyphenylene ether resin forming the dispersed phase and 100 parts by weight of the component (a) and the component (b). Block A and at least one polymer block B mainly composed of a conjugated diene compound having a total amount of 1,2-vinyl bonds and 3,4-vinyl bonds in the conjugated diene compound of 45 to 90%. 5-30 parts by weight of a hydrogenated block copolymer obtained by hydrogenating the block copolymer, and (d) an average diameter of 3-20 μm That fibrous inorganic filler and (e) an average flake diameter of a plate like inorganic filler is 10~700μm, (d) and the component 30 parts by weight or more, and (d) the total of component and component (e) 50 to 140 parts by weight, a resin composition in which the weight ratio of the component (d) to the component (e) is 70/30 to 30/70,
[2] The melt flow rate (MFR) (230 ° C., load 21.2 N) of the crystalline propylene homopolymer or / and the crystalline propylene-ethylene block copolymer resin as the component (a) is 0.1 to 30 g / 10. The resin composition according to [1], wherein
[3] The component (c) is a hydrogenated product of a styrene-butadiene block copolymer comprising a styrene polymer block (A) and a butadiene polymer block (B), and is one of the butadiene polymer blocks (B). The resin composition according to [1] or [2], wherein the total amount of, 2-vinyl bond and 3,4-vinyl bond is 65 to 90%,
[4] The resin composition according to any one of [1] to [3], wherein the component (d) is a glass fiber,
[5] The resin composition according to any one of [1] to [4], wherein the component (e) is at least one selected from mica, glass flakes, graphite, and talc.
[6] The total amount of component (b) and the component (a) and part or all of component (c) are melt-kneaded, and with respect to the melt-kneaded product, component (a), the remaining amount of component (c) and (D) Component, (e) Component is supplied, Furthermore melt-kneading, The manufacturing method of the resin composition of any one of [1]-[5] characterized by the above-mentioned,
[7] The total amount of component (b) and part or all of component (c) are melt-kneaded, and the total amount of component (a), the remaining amount of component (c), and (d) The method for producing a resin composition according to any one of [1] to [5], wherein the component, (e) component is supplied and further melt-kneaded
[8] A resin composition obtained by the production method described in [6] or [7],
[9] A container having water vapor permeability resistance, molded using the resin composition according to any one of [1] to [5].

  The resin composition of the present invention is composed of a polypropylene-based resin, a polyphenylene ether-based resin, a hydrogenated block copolymer, a fibrous inorganic filler, and a plate-like inorganic filler, and contains the fibrous inorganic filler and the plate-like inorganic filler used. It is difficult to obtain by the prior art by specifying the amount and weight ratio, and comprises a resin composition excellent in the balance of warpage, molding cycle, rigidity, heat resistance, and water vapor permeability resistance, and the resin composition. A molded body can be provided.

  As the polypropylene resin used as the component (a) forming the matrix of the resin composition of the present invention, the crystalline propylene homopolymer or 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 is preferable, and a mixture of the crystalline propylene homopolymer and the crystalline propylene-ethylene block copolymer may be used. Such a polypropylene resin is usually used 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 at a polymerization temperature of 0 to 100 ° C. and a polymerization pressure of 3 to 100. Obtained by polymerization in the range of atmospheric pressure.

  At this time, a chain transfer agent such as hydrogen can be added to adjust the molecular weight of the polymer, and the polymerization method can be either a batch type or a continuous type, butane, pentane, hexane, heptane. Further, methods such as solution polymerization in a solvent such as octane and slurry polymerization can also be selected. Furthermore, bulk polymerization in a monomer in the absence of a solvent, gas phase polymerization method in a gaseous monomer, and the like can be applied. Furthermore, in order to increase the isotacticity and polymerization activity of the polypropylene obtained in addition to the polymerization catalyst described above, an electron donating compound can be used as an internal donor component or an external donor component as a third component. A well-known thing can be used as an electron-donating compound.

  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, and phosphoric acid derivatives such as hexamethylphosphoric triamide And alkoxyester compounds, aromatic monocarboxylic acid esters and / or aromatic alkylalkoxysilanes, aliphatic hydrocarbon alkoxysilanes, various ether compounds, various alcohols and / or various phenols.

  As long as the polypropylene resin used in the present invention is obtained by the above-described method, it can be used either alone or in combination, having any crystallinity and melting point. The polypropylene resin has a melt flow rate (MFR) (230 ° C., load 21.2 N) of preferably 0.01 to 300 g / 10 minutes, more preferably 0.1 to 100 g / 10 minutes, particularly preferably. The range is 0.1 to 30 g / 10 minutes. Moreover, if it is MFR of these ranges, it can be used individually or in combination.

  Furthermore, in order to improve the adhesion between the filler described later and the polypropylene resin described above, in addition to the polypropylene resin described above, the polypropylene resin and an α, β-unsaturated carboxylic acid or derivative thereof are generated as radicals. A known modification (the α, β-unsaturated carboxylic acid or its derivative is 0.01 to 0.01%) obtained by reacting at a temperature of 30 to 350 ° C. in the molten state or in the solution state in the presence or absence of an agent. A 10% by weight graft or addition) polypropylene resin may be used, and a mixture of the above-described polypropylene resin and the modified polypropylene resin in any ratio may be used.

  The polyphenylene ether resin (hereinafter simply referred to as PPE) used as the component (b) in the present invention is a homopolymer and / or copolymer having a repeating unit structure represented by the following formula (1). The reduced viscosity (0.5 g / dl, chloroform solution, measured at 30 ° C.) is preferably in the range of 0.15 to 2.5, more preferably 0.30 to 2.00, still more preferably 0. The range is from 35 to 2.00. The polyphenylene ether resin is a compound known per se.

(Where R ₁ , R ₂ , R ₃ , and R ₄ are each hydrogen, halogen, primary or secondary lower alkyl group having 1 to 7 carbon atoms, phenyl group, haloalkyl group, aminoalkyl group. A hydrocarbonoxy group or a halohydrocarbonoxy group in which at least two carbon atoms separate a halogen atom and an oxygen atom, and may be the same or different from each other)

  Specific examples of the PPE include poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), and poly (2-methyl ether). -6-phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether) and the like, and 2,6-dimethylphenol and other phenols (for example, 2,6- Polyphenylene ether copolymers such as copolymers with 3,6-trimethylphenol and 2-methyl-6-butylphenol) may also be mentioned.

  Of these, poly (2,6-dimethyl-1,4-phenylene ether) and a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol are preferable, and poly (2,6-dimethyl-1 , 4-phenylene ether). The method for producing such PPE is not particularly limited as long as it is a known method. For example, it can be easily produced by oxidative polymerization of 2,6-xylenol using, for example, a complex of cuprous salt and amine by Hay described in US Pat. No. 3,306,874 as a catalyst. Nos. 3257357 and 3257358, Japanese Patent Publication No. 52-17880, Japanese Patent Application Laid-Open Nos. 50-51197 and 63-152628, and the like.

  In addition to the above-mentioned PPE, the PPE used in the present invention is 80 to 350 in the molten state, in the solution state, and in the slurry state in the presence or absence of the radical generator. It may be a known modified PPE obtained by reacting at a temperature of ° C (the styrenic monomer or derivative thereof is 0.01 to 10 wt% grafted or added), and the PPE and the modified PPE It may be a mixture in an arbitrary ratio. In addition to the above-mentioned PPE, the PPE used in the present invention is preferably one in which polystyrene, syndiotactic polystyrene or high impact polystyrene is added in an amount not exceeding 400 parts by weight with respect to 100 parts by weight of these PPEs. it can.

Next, the hydrogenated block copolymer which can be used as the component (c) in the present invention is an admixture and an impact resistance imparting agent for the polypropylene resin as the component (a) and the polyphenylene ether resin as the component (b). A conjugated diene compound having a total amount of 1,2-vinyl bonds and 3,4-vinyl bonds of 45 to 90%. A hydrogenated block copolymer obtained by hydrogenating at least 50% of double bonds derived from such a conjugated diene compound with a block copolymer comprising at least one polymer block B mainly composed of a diene compound. is there.
For example, vinyl aromatic compound-conjugated diene compound having a structure such as A-B, A-B-A, B-A-B-A, (A-B-) ₄ Si, A-B-A-B-A, etc. It is a hydrogenated product of a block copolymer.

  The hydrogenated block copolymer of component (c) contains 20 to 95% by weight, more preferably 30 to 80% by weight, of a vinyl aromatic compound to which the block copolymer before hydrogenation is bonded. In addition, referring to the block structure, the polymer block A mainly composed of a vinyl aromatic compound contains a homopolymer block of a vinyl aromatic compound or a vinyl aromatic compound in an amount of more than 50% by weight, preferably 70% by weight or more. It has a copolymer block structure of a vinyl aromatic compound and a conjugated diene compound, and a polymer block mainly composed of a conjugated diene compound is a homopolymer block of a conjugated diene compound or a conjugated diene compound. It has a structure of a copolymer block of a conjugated diene compound and a vinyl aromatic compound that is contained in an amount exceeding 50% by weight and preferably 70% by weight or more.

  Further, the polymer block A mainly composed of these vinyl aromatic compounds and the polymer block B mainly composed of conjugated diene compounds are distributions of vinyl aromatic compounds or conjugated diene compounds in the molecular chains in the respective polymer blocks. May be random, tapered (in which the monomer component increases or decreases along the molecular chain), partially in the form of a block, or any combination thereof, and the polymer block A mainly composed of the vinyl aromatic compound When there are two or more polymer blocks B mainly composed of the conjugated diene compound, the polymer blocks may have the same structure or different structures.

  As the vinyl aromatic compound constituting the block copolymer, for example, one or more kinds can be selected from styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, diphenylethylene, and the like. Of these, styrene is preferred. Further, as the conjugated diene compound, for example, one or two or more kinds are selected from butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, etc., among which butadiene, isoprene and These combinations are preferred.

  A polymer block mainly composed of a conjugated diene compound has a microstructure (bonded form of the conjugated diene compound) in the block, which is the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds (hereinafter vinyl bond amounts). In terms of miscibility, it is 45 to 90%, preferably 50 to 85%. In the polymer block mainly composed of butadiene, the vinyl bond content is preferably 65 to 90%, and in that case, the vinyl aromatic compound is preferably styrene. If the total vinyl bond content is less than 45%, the dispersibility of the polyphenylene ether resin dispersed in the resulting resin composition is undesirably deteriorated. Even if the total vinyl bond content exceeds 90%, the improvement in dispersibility of the polyphenylene ether resin is not remarkable. The bonding form of these conjugated diene compounds can be usually known by an infrared spectrophotometer, NMR or the like.

  The number average molecular weight of the block copolymer having the above structure is in the range of 5,000 to 1,000,000, preferably 10,000 to 800,000, more preferably 30,000 to 500,000. The molecular weight distribution [ratio of weight average molecular weight (Mw) and number average molecular weight (Mn) measured by gel permeation chromatography] is 10 or less. Further, the molecular structure of the block copolymer may be linear, branched, radial, or any combination thereof.

  The block copolymer having such a structure is a hydrogenated block copolymer obtained by hydrogenating the aliphatic double bond of the polymer block B mainly composed of the conjugated diene compound of the block copolymer described above. It can be used as the component (c). The hydrogenation rate of such aliphatic double bonds is 50% or more, preferably 80% or more, more preferably 90% or more. This hydrogenation rate can usually be known by an infrared spectrophotometer, NMR or the like.

  These hydrogenated block copolymers of the component (c) may be obtained by any production method as long as they have the structure described above. Examples of known production methods include, for example, JP-A-47-11486, JP-A-49-66743, JP-A-50-75651, JP-A-54-126255, JP-A-54-126255. No. 56-10542, JP-A-56-62847, JP-A-56-1000084, JP-A-2-300218, British Patent No. 1130770, US Pat. Nos. 3,281,383 and 3,639,517. And methods described in British Patent No. 1020720 and US Pat. Nos. 3,333,024 and 4,501,857.

  The hydrogenated block copolymer of component (c) used in the present invention includes the hydrogenated block copolymer and an α, β-unsaturated carboxylic acid or derivative thereof in addition to the hydrogenated block copolymer described above. A modified hydrogenated block obtained by reacting (an ester compound or an acid anhydride compound) in the presence of a radical generator in the presence or absence of a radical generator in a molten state, a solution state, or a slurry state at a temperature of 80 to 350 ° C. 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 weight. . Further, it may be a mixture in any proportion of the above-mentioned hydrogenated block copolymer and the modified hydrogenated block copolymer.

Next, there is no restriction | limiting in the shape of the fibrous inorganic filler used as (d) component of this invention, A well-known fibrous inorganic filler can be used. In addition, surface treatment according to the component (d) of the present invention to be used, for example, various coupling agents such as silane type and titanate type and sizing agents treated with epoxy resin, urethane resin, etc. should be used. Is preferred.
Examples of fibrous inorganic fillers include glass fibers, carbon fibers, whiskers such as potassium titanate, wollastonite, and the like. These fibrous inorganic fillers have an average fiber diameter of 3 to 20 μm, more preferably 5 to 20 μm, from the viewpoint of the reinforcing effect.

  Next, examples of the plate-like inorganic filler of the component (e) of the present invention include glass flakes, mica, talc, and graphite. These plate-like inorganic fillers have an average flake diameter of 10 to 700 μm, more preferably 80 to 680 μm, and particularly preferably 100 to 680 μm, from the viewpoint of warpage and reinforcing effect. Further, the plate-like inorganic filler imparts excellent warpage, molding cycle, rigidity, heat resistance, and water vapor permeability resistance to the resin composition of the present invention due to a synergistic effect with the above-described fibrous inorganic filler.

  The resin composition of the present invention is composed of the above components (a) to (e) as basic components. In the present invention, the amount of component (a) is 45 to 95 parts by weight from the viewpoint of fluidity, solvent resistance and heat resistance, with the matrix being a polypropylene resin. Next, the compounding quantity of (b) component is 55-5 weight part from a viewpoint of fluidity | liquidity, solvent resistance, and heat resistance, when a polyphenylene ether resin forms a dispersed phase.

Next, the blending amount of the component (c) is 5 to 30 from the viewpoint of imparting impact resistance and heat resistance, solvent resistance, rigidity and mechanical strength to 100 parts by weight of the component (a) and component (b). Parts by weight.
Next, the total blending amount of the component (d) and the component (e) is in terms of warpage of the molded product, molding cycle, rigidity, heat resistance and water vapor permeability resistance with respect to 100 parts by weight of the component (a) and the component (b). From 50 to 140 parts by weight and the weight ratio (d) / (e) is 70/30 to 30/70, preferably 65/35 to 35/65, more preferably 60/40 to 40/60. Selected from the range. When the weight ratio of the component (d) to the component (e) is outside the above range, for example, when the component (e) is large and the component (d) is small, the warpage and the molding cycle are excellent, but the reinforcing effect and heat resistance are excellent. Decreases. Moreover, when there are many (d) components and there are few (e) components, the improvement effect of curvature will fall and it is unpreferable.

  In the present invention, in addition to the above-described components, other additional components, for example, a vinyl aromatic compound-conjugated diene compound block copolymer and an olefin-based elastomer, are added as necessary without departing from the characteristics and effects of the present invention. , Antioxidants, metal deactivators, heat stabilizers, flame retardants (organic phosphate ester compounds, ammonium polyphosphate compounds, aromatic halogen flame retardants, silicone flame retardants, etc.), fluoropolymers, plastics Agents (low molecular weight polyethylene, epoxidized soybean oil, polyethylene glycol, fatty acid esters, etc.), flame retardant aids such as antimony trioxide, weathering (light) improvers, polyolefin nucleating agents, slip agents, inorganic or organic Fillers and reinforcements (polyacrylonitrile fiber, carbon black, titanium oxide, calcium carbonate, conductive metal fiber, conductive catalyst Carbon black, etc.), various coloring agents, may be added, such as a release agent.

  The resin composition of the present invention can be produced using various melt mixers and kneading extruders, and examples of the melt kneading machine for performing these methods include, for example, a single screw extruder and a multi-screw including a twin screw extruder. Examples thereof include a heat-melting and kneading machine such as an extruder, roll, kneader, Brabender plastograph, Banbury mixer, etc. Among them, a melt-kneading method using a twin-screw extruder is most preferable. Specific examples include the ZSK series manufactured by WERNER & PFLIDEERER, the TEM series manufactured by Toshiba Machine Co., Ltd., and the TEX series manufactured by Nippon Steel Works.

  A preferred embodiment of the present invention using an extruder will be described below. The L / D (barrel effective length / barrel inner diameter) of the extruder is in the range of 20 to 75, 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. In particular, a kneading section is provided upstream of the first vacuum vent, a kneading section is provided between the first vacuum vent and the second raw material supply port, and kneading is performed between the second raw material supply port and the second vacuum vent. A section with a kneading section, a kneading section upstream of the first vacuum vent, a kneading section between the first vacuum vent and the second raw material supply port, and a second raw material supply port and a third raw material supply More preferably, a kneading section is provided in the mouth, and a kneading section is provided between the second raw material supply port and the second vacuum vent. The raw material supply method to the second and third raw material supply ports is not particularly limited, but it is forced from the extruder side opening port rather than the simple addition supply from the extruder second and third supply port opening ports. It is more stable and preferable to supply using a side feeder.

  In particular, when a powder, filler or the like is included as in the resin composition of the present invention, the forced side feeder supplied from the extruder side is more preferable, and the upper open ports of the extruder second and third supply ports Can be opened to remove the air to be carried. The melt-kneading temperature and screw rotation speed at this time are not particularly limited, but can normally be arbitrarily selected from a melt-kneading temperature of 200 to 370 ° C. and a screw rotation speed of 100 to 1200 rpm.

  The particularly preferred production method of the present invention is a method in which the total amount of the component (b), the component (a), and a part or the total amount of the component (c) are melt-kneaded, and the component (a), (C) The remaining amount of the component and the method of supplying the component (d) and the component (e) and continuing the melt-kneading, or melt-kneading the total amount of the component (b) and the part or all of the component (c) In this method, the total amount of the component (a), the remaining amount of the component (c) and the component (d) and the component (e) are supplied to the melt-kneaded product, and the melt-kneading is continued. By these production methods, the obtained resin composition can obtain a dispersion form in which (b) component, (c) component mixture and (d) component, and (e) component are excellent in component (a), By minimizing crushing during melting and kneading of the component (d) and the component (e), a resin composition excellent in warpage, rigidity and heat resistance of the molded product can be obtained.

  A more specific production method is as follows: From the first raw material supply port of the twin screw extruder, the total amount of component (b) and a part or the total amount of 45 to 95% by weight of component (a), preferably the total amount of component (a) 5 to 100% by weight of the total amount of (a) component and (b) component is 100 parts by weight, part or all of (c) component 5 to 30 parts by weight, preferably the total amount of component (c) 30 to 100% by weight of the component (a), the component (b), and the component (c) under the melt-kneaded state of the component (a) and the component (c) from the second raw material supply port. In this method, the remaining amount and the total amount of the component (d) and the component (e) are supplied using a forced side feeder, and the melt kneading is continued.

In addition, from the first raw material supply port of the twin screw extruder, the total amount of component (b) and part or all of component (a) 45 to 95% by weight, preferably 5 to 100% by weight of the total amount of component (a) And (a) component and (b) total 100 parts by weight of component (c) 5 to 30 parts by weight of part or all of component, preferably 30 to 100% by weight of total amount of component (c) In the melt kneaded state of these components (a), (b), and (c), the remaining amount of component (a), component (c), and (e) There is a method in which the total amount of the component (d) is supplied from the component and third raw material supply port using a forced side feeder, and the melt kneading is continued. The resin composition obtained from these production methods can obtain a uniform dispersed form in which the component (b), the component (c), the component (d) and the component (e) are excellent in the component (a). The effect of adding the component (e) can be exhibited most significantly, and the crushing of the component (d) during melt-kneading can be minimized. Taking such a production method is very important in obtaining a resin composition having excellent warpage, rigidity and heat resistance of the molded product.
On the other hand, the molded product of the resin composition obtained when all the components (a) to (e) are supplied from the first raw material supply port is insufficient in warpage, rigidity and heat resistance.

The resin composition of the present invention thus obtained can be molded as molded parts of various parts 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, and other exterior parts, It is suitable for interior parts such as instrument panels, console boxes and trims, as well as secondary battery battery case parts mounted on automobiles, electric cars and hybrid electric cars.
It can also be used suitably as an interior / exterior part of electrical equipment. Specifically, various computers and peripheral equipment, other office automation equipment, televisions, videos, various disk player cabinets, chassis, refrigerators, air conditioners, liquid crystal projectors. In industrial parts, it is suitable for parts such as various pump casings and boiler casings.

The present invention will be described in more detail by way of examples, but is not limited by these examples.
First, the raw material components used in Examples and Comparative Examples are described.

<Raw ingredient>
(A) Component: Polypropylene resin (a-1) Propylene homopolymer Melting point = 167 ° C., MFR = 6
(A-2) Propylene homopolymer Melting point = 168 ° C., MFR = 2.8
(A-3) Propylene copolymer Melting point = 170 ° C., MFR = 2.5
(A-4) Maleic anhydride-modified polypropylene Melting point = 163 ° C., MFR = 100
The MFR of polypropylene was measured in accordance with ASTM D-1238 at 230 ° C. and a load of 21.2 N.
(B) Component: PPE
PPE having a reduced viscosity of 0.43 obtained by oxidative polymerization of 2,6-xylenol
Component (c): Hydrogenated block copolymer Polystyrene (1) -hydrogenated polybutadiene-polystyrene (2) structure, 43% bonded styrene, 95,000 number average molecular weight, polybutadiene before hydrogenation 80% of the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds, polystyrene (1) number average molecular weight 30,000, polystyrene (2) number average molecular weight 10,000, polybutadiene part hydrogenation Hydrogenated product of styrene-butadiene block copolymer with a 99.9% rate

(D) Component: Fibrous inorganic filler (d-1) Glass fiber having an average diameter of 13 μm and a chop length of 3.5 mm (d-2) Basic magnesium sulfate having a diameter of 0.5 to 1.0 μm and a fiber length of 10 to 30 μm Inorganic fiber (e) component: plate-like inorganic filler (e-1) Mica having an average flake diameter of 280 μm (e-2) Graphite having an average flake diameter of 130 μm (e-3) Glass flake having an average flake diameter of 130 μm (e-4) Mica with an average flake diameter of 650 μm (e-5) Graphite with an average flake diameter of 5 μm

[Examples 1 to 10 and Comparative Examples 1 to 4]
Using a twin-screw extruder ZSK-25 (manufactured by WERNER & PFLIDELER), a first raw material supply port is provided upstream of the flow direction of the raw material, a second raw material supply port is provided downstream of this, and a vacuum vent is provided downstream thereof. It was. Moreover, the raw material supply method to a 2nd supply port is supplied using a forced side feeder from an extruder side open port. Using the extruder set as described above, (a) polypropylene, (b) polyphenylene ether, (c) hydrogenated block copolymer as an admixture, (d) fibrous inorganic filler, (e) plate-like inorganic The filler was blended with the composition shown in Table 1, and 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 12 kg / hour to obtain pellets.

  Also, using the resin pellet obtained above, it is supplied to a screw in-line type injection molding machine set at 240 to 280 ° C., and under the condition of a mold temperature of 60 ° C., a test piece for measuring flexural modulus and for measuring deflection temperature under load. A test piece was injection-molded, and left in an environment of 80 ° C. for 24 hours using a gear oven to perform a heat history treatment. The molded product for measuring warpage is supplied to a screw in-line injection molding machine in which resin pellets are set at 190 to 270 ° C., and is a box shape having a length of 100 mm × width of 75 mm × height of 42 mm under the condition of a mold temperature of 40 ° C. The molded product was molded. The mold cooling time for the box-shaped molded product was set to 10 seconds, 30 seconds, and 60 seconds.

Next, the flexural modulus (ASTM D-790) and the deflection temperature under load (ASTM D-648) were measured using these test pieces. Warpage was performed by allowing the box-shaped molded article for each cooling time to stand for 24 hours under the conditions of a temperature of 23 ° C. and a humidity of 50%, and measuring the maximum displacement of the inner warp.
The molding cycle was evaluated according to the following three steps using the mold cooling time required until the amount of warpage of the obtained molded product to be 0.60 mm or less as an index.
◎: Cooling time 30 seconds or less ○: Cooling time 31 to 60 seconds or less X: Cooling time 61 seconds or more

For water vapor permeability resistance (JIS K7129), a water vapor permeability [g / (m ² · 24Hr)] was measured from a water vapor permeability test at 40 ° C. using a 1 mm thick flat plate obtained by injection molding.
In addition, as a comprehensive evaluation, the balance of warpage, molding cycle, rigidity, heat resistance, and water vapor permeability was compared, and the case where the balance was good was evaluated as ◯ and the case where it was bad was evaluated as ×.

  The above results are also shown in Table 1. From Table 1, the resin composition of the present invention is excellent in warpage, molding cycle, rigidity, heat resistance, and water vapor permeability at the same time by using a fibrous or plate-like inorganic filler in combination, but the composition of the present invention is in the range. When it was outside, it became clear that the warpage, molding cycle, rigidity, heat resistance and water vapor permeability resistance could not be improved at the same time.

  Since the resin composition obtained in the present invention and the resin composition are excellent in warpage, molding cycle, rigidity, heat resistance and water vapor permeability of a molded product, they are suitably used for applications requiring these characteristics. be able to.

Claims (9)

(A) Crystalline propylene homopolymer and maleic anhydride modified polypropylene forming a matrix phase , or 45 to 95 parts by weight of crystalline propylene-ethylene block copolymer resin and maleic anhydride modified polypropylene, (b) Dispersed phase (C) at least one polymer block A mainly composed of a vinyl aromatic compound, based on 55 to 5 parts by weight of the polyphenylene ether resin to be formed and 100 parts by weight of the total of the component (a) and the component (b) A block copolymer consisting of at least one polymer block B mainly composed of a conjugated diene compound in which the total amount of 1,2-vinyl bonds and 3,4-vinyl bonds in the conjugated diene compound is 45 to 90%. 5-30 parts by weight of a hydrogenated block copolymer obtained by hydrogenating the coalescence, and (d) an average diameter of 3-20 μm.維状inorganic filler and (e) an average flake diameter of a plate like inorganic filler is 10~700μm, (d) and the component 30 parts by weight or more, and component (d) and (e) the total of component 50 -140 weight part, The resin composition whose weight ratio of (d) component and (e) component consists of 70 / 30-30 / 70.   The melt flow rate (MFR) (230 ° C., load 21.2 N) of the crystalline propylene homopolymer or / and the crystalline propylene-ethylene block copolymer resin as component (a) is 0.1 to 30 g / 10 min. The resin composition according to claim 1.   The component (c) is a hydrogenated product of a styrene-butadiene block copolymer comprising a styrene polymer block (A) and a butadiene polymer block (B), and 1,2- of the butadiene polymer block (B). 3. The resin composition according to claim 1, wherein the total amount of vinyl bonds and 3,4-vinyl bonds is 65 to 90%.   (D) A component is glass fiber, The resin composition of any one of Claims 1-3 characterized by the above-mentioned.   (E) A component is at least 1 sort (s) chosen from mica, glass flakes, graphite, and talc, The resin composition of any one of Claims 1-4 characterized by the above-mentioned.   (B) The total amount of component and (a) component, part or all of (c) component are melt-kneaded, and the melt-kneaded product is mixed with (a) component, (c) remaining amount of component and (d) The method for producing a resin composition according to claim 1, wherein the component (e) is supplied and further melt-kneaded.   (B) The total amount of component and part or all of component (c) are melt-kneaded, and the total amount of component (a), the remaining amount of component (c) and the component (d), ( The method for producing a resin composition according to any one of claims 1 to 5, wherein the component e) is supplied and further melt-kneaded.   A resin composition obtained by the production method according to claim 6.   A container having water vapor permeability resistance, molded using the resin composition according to any one of claims 1 to 5.