JP4672682B2 - Conductive resin composition - Google Patents

Description

The present invention relates to a resin molded body. More specifically, the present invention includes a polyamide (A) comprising two or more different polyamide components, a polyphenylene ether (B) and a specific partially hydrogenated block copolymer (C), wherein the polyamide (A) A continuous phase is formed, the polyphenylene ether (B) is dispersed in the continuous phase to form a dispersed phase, and the partially hydrogenated block copolymer is composed of the continuous phase of the polyamide (A) and the polyphenylene ether ( The surface area of the polyamide (A) present in at least one phase selected from the group consisting of the dispersed phase of B) and exposed on the surface of the molded body is 80% or more with respect to the total surface area of the molded body It is related with the resin molding characterized by being. The resin molded body of the present invention has a matte surface, adhesion with a coated film after coating (hereinafter, simply referred to as “coated film adhesion”) and coated film clarity (gloss of coated film). Also excellent. The present invention also provides a conductive resin composition comprising polyamide (A), polyphenylene ether (B), specific block copolymer (C), conductive carbon material (D) and wollastonite particles (E). Also related. When a molded article is produced using the conductive resin composition of the present invention, the obtained molded article is not only superior in surface matteness, coating adhesion after coating, and coating clarity, but also in automobiles. A molded article having a sufficiently low linear expansion coefficient, which is a particularly important characteristic in a large molded article such as a fender or an automobile back door, can be obtained. The resin molded body of the present invention and the molded body obtained by using the conductive resin composition of the present invention are not only automobile exterior parts, but also electric / electronic parts, OA parts, machine parts, and motorcycle / car electrical equipments. It can be suitably used in a wide range of fields such as parts and interior parts.

Polyphenylene ether has excellent mechanical properties, electrical properties such as dielectric constant and dielectric loss tangent, and heat resistance, and has excellent dimensional stability, so it is used in a wide range of applications. In order to improve this, Patent Document 1 proposes a technique of blending polyamide, and after that, new techniques are disclosed in Patent Document 2, Patent Document 3, and Patent Document 4, and now, It is a material used for a wide variety of applications including exterior parts.
In many automotive exterior parts applications, painting is often applied, and the performance of high adhesion to the coating film (hereinafter referred to as “coating film adhesion”) is an important factor in material selection. Yes.
A technique for imparting paintability to a material composed of polyamide and polyphenylene ether has been studied in the past. For example, in Patent Document 5 (corresponding to US Pat. No. 5,556,693), a specific terpene phenol resin is added. Thus, a technique for improving coating film adhesion is disclosed. Patent Document 6 discloses a technique that enables a resin molded product to be painted without applying a primer by post-processing with a surfactant.

Japanese Examined Patent Publication No. 45-000997 U.S. Pat. No. 0431508 U.S. Pat. No. 4,732,938 US Pat. No. 4,659,760 Japanese Patent Application Laid-Open No. 08-109324 Japanese Patent Laid-Open No. 03-143571

However, in these technologies, additives are used to improve the adhesion of the coating film, and there are adverse effects such as a decrease in heat resistance due to the addition of additives and moisture absorption after painting. There has been a demand for a technique for improving the paintability without any problems.
Moreover, a low linear expansion coefficient is mentioned as one of the characteristics required for large molded articles such as automobile fenders and automobile back doors. There is a gap for opening and closing the door between the fender and the door of the car, but when a fender is manufactured using a material with large linear expansion, a phenomenon occurs in which the width of the gap changes depending on the temperature. However, improvements to materials having a lower linear expansion coefficient are required.
In order to cope with these characteristics, it is generally possible to improve by adding an organic or inorganic filler. However, by blending an organic or inorganic filler, the filler is likely to be present on the surface layer portion of the molded body, and the coating film adhesion after coating and the sharpness of the coating film are inferior. Therefore, it has been demanded to simultaneously improve the coefficient of linear expansion, the adhesion of the coating film, and the sharpness of the coating film.

The present inventors have solved the above-mentioned problems and made it possible to produce a molded article superior in surface matteness, paint film adhesion, and paint clarity after painting without using the additives as described above. In order to develop a polyamide-polyphenylene ether alloy, the inventors have intensively studied. As a result, in the molded body composed of polyamide, polyphenylene ether and partially hydrogenated aromatic vinyl / conjugated diene block copolymer, by controlling the area ratio of polyamide on the molded body surface to a specific value or more, It was surprisingly found that the above purpose could be achieved. Furthermore, the present inventors provide a conductive resin composition comprising polyamide (A), polyphenylene ether (B), specific block copolymer (C), conductive carbon material (D) and wollastonite particles (E). When a molded product is produced using a product, it is possible to obtain a molded product having a low coefficient of linear expansion as well as excellent surface matteness, coating adhesion after coating, and coating sharpness without using additives. It was found that it can be obtained. The present invention has been completed based on these findings.
Accordingly, one object of the present invention is to provide a resin molded article having excellent surface matte properties, coating film adhesion after coating, and coating film sharpness.
Another object of the present invention is to provide a conductive resin composition capable of forming a molded article having a low coefficient of linear expansion, as well as being excellent in surface matteness, coating adhesion after coating, and coating sharpness. Is to provide things.
The above and other objects, features and advantages of the present invention will become apparent from the following detailed description and claims.

According to the present invention,
Polyamide (A) comprising two or more different polyamide components,
Polyphenylene ether (B) and at least one partially hydrogenated block copolymer (C)
A resin molded body comprising
The partially hydrogenated block copolymer (C) is independently at least one aromatic vinyl polymer block mainly composed of an aromatic vinyl monomer unit and at least mainly composed of a conjugated diene monomer unit. It is obtained by partially hydrogenating a non-hydrogenated block copolymer comprising one conjugated diene polymer block, and the partially hydrogenated block copolymer (C) has at least one number average molecular weight of 200. , 1,000 to 300,000 partially hydrogenated block copolymer (C-1),
The polyamide (A) forms a continuous phase, the polyphenylene ether (B) is dispersed in the continuous phase to form a dispersed phase, and the partially hydrogenated block copolymer is a continuous phase of the polyamide (A). Present in at least one phase selected from the group consisting of a phase and a dispersed phase of the polyphenylene ether (B),
The polyamide (A) is exposed on the surface of the molded body, and the surface area of the polyamide (A) exposed on the surface of the molded body is 80% or more with respect to the total surface area of the molded body.
A resin molded body characterized by the above is provided.

In order to facilitate understanding of the present invention, the basic features and preferred embodiments of the present invention are listed below.
1. Polyamide (A),
Polyphenylene ether (B),
A block copolymer (C) comprising at least one aromatic vinyl polymer block mainly comprising an aromatic vinyl monomer unit and at least one conjugated diene polymer block mainly comprising a conjugated diene monomer unit;
Conductive carbon material (D) and wollastonite particles (E)
A conductive resin composition comprising:
2. A master batch obtained by dispersing the conductive carbon material (D) in the polyamide (A) is mixed with the polyphenylene ether (B), the block copolymer (C), the wollastonite particles (E), and optionally. Is produced by melt-kneading with at least one selected from the group consisting of an additional amount of the polyamide (A) and an additional amount of the conductive carbon material (D), and the conductive carbon material (D) is electrically conductive. 1. At least one selected from the group consisting of carbon black, carbon fibrils, and carbon nanotubes. The conductive resin composition described in 1.
3. 1. The average particle diameter of the wollastonite particles (E) is 2 to 9 μm. The conductive resin composition described in 1.
4). The wollastonite particles (E) include particles having an aspect ratio of 5 or more and particles having an aspect ratio of less than 5, and the amount of particles having an aspect ratio of 5 or more is 50 with respect to the total weight of the wollastonite particles (E). The above-mentioned 1. characterized by being at least wt%. The conductive resin composition described in 1.

When a molded body is produced using the conductive resin composition of the present invention, the obtained molded body is excellent in surface matting properties, coating film adhesion after coating, and coating film sharpness.
Hereinafter, the present invention will be described in detail.
In the first aspect of the present invention,
Polyamide (A) comprising two or more different polyamide components,
Polyphenylene ether (B) and at least one specific partially hydrogenated block copolymer (C)
A resin molded body comprising
The polyamide (A) forms a continuous phase, the polyphenylene ether (B) is dispersed in the continuous phase to form a dispersed phase, and the partially hydrogenated block copolymer is a continuous phase of the polyamide (A). Present in at least one phase selected from the group consisting of a phase and a dispersed phase of the polyphenylene ether (B),
The polyamide (A) is exposed on the surface of the molded body, and the surface area of the polyamide (A) exposed on the surface of the molded body is 80% or more with respect to the total surface area of the molded body.
A resin molded body characterized by the above is provided.
Any kind of polyamide (A) that can be used in the resin molded body of the present invention is used as long as it has an amide bond {—NH—C (═O) —} in the polymer repeating structure. Is possible.

  In general, polyamides are obtained by ring-opening polymerization of lactams, polycondensation of diamine and dicarboxylic acid, polycondensation of ω-aminocarboxylic acid, but are not limited thereto. The diamines are roughly classified into aliphatic, alicyclic and aromatic diamines, and specific examples include tetramethylene diamine, hexamethylene diamine, undecamethylene diamine, dodecamethylene diamine, tridecamethylene diamine, 2, 2 , 4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, 1,3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, m-phenylenediamine, p -Phenylenediamine, m-xylylenediamine, p-xylylenediamine and the like.

Dicarboxylic acids are roughly classified into aliphatic, alicyclic and aromatic dicarboxylic acids. Specific examples include adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 1,1,3-tridecane. Examples include diacid, 1,3-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, dimer acid and the like.
Specific examples of lactams include ε-caprolactam, enantolactam, and ω-laurolactam.
Specific examples of the ω-aminocarboxylic acid include ε-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, 13- And aminotridecanoic acid.
In the resin molded product of the present invention, these lactams, diamines, dicarboxylic acids and ω-aminocarboxylic acids can be obtained by performing polycondensation on polyamide homopolymers obtained by using them alone or in a mixture of two or more. Any of the copolymerized polyamides can be used.
Further, those obtained by polymerizing these lactams, diamines, dicarboxylic acids, and ω-aminocarboxylic acids up to a low molecular weight oligomer stage in a polymerization reactor and increasing the molecular weight in an extruder or the like can be suitably used.

  Specific examples of polyamide resins that can be usefully used in the present invention include polyamide 6, polyamide 6,6, polyamide 4,6, polyamide 11, polyamide 12, polyamide 6,10, polyamide 6,12, polyamide 6/6. , 6, polyamide 6 / 6,12, polyamide MXD (m-xylylenediamine), 6, polyamide 6, T, polyamide 6, I, polyamide 6/6, T, polyamide 6/6, I, polyamide 6,6 / 6, T, polyamide 6,6 / 6, I, polyamide 6/6, T / 6, I, polyamide 6,6 / 6, T / 6, I, polyamide 6/12/6, T, polyamide 6, 6/12/6, T, polyamide 6/12/6, I, polyamide 6, 6/12/6, I, and the like, and a poly or blended or copolymerized polyamide with an extruder Bromide acids can also be used.

In the resin molding of the present invention, it is necessary to use two or more polyamide components as the polyamide (A), and it is preferable to use two or more polyamide components having different viscosities. In this case, using the viscosity number measured in 96% sulfuric acid according to ISO 307, for example, a combination of a polyamide component having a viscosity number of 80 ml / g and a polyamide component having a viscosity number of 150 ml / g, a polyamide component having a viscosity number of 120 ml / g, Examples thereof include a combination with a polyamide component having a viscosity number of 115 ml / g. When such different polyamide components are used as a mixture, the viscosity number is preferably in the range of 90 to 130 ml / g. More preferably, it is the range of 100-125 ml / g. Whether or not the viscosity number of the mixture is within the above range can be confirmed by dissolving each polyamide component in 96% sulfuric acid at a mixing weight ratio and measuring the viscosity number according to ISO307. . By using a combination of polyamide components having different molecular weights as described above, it becomes possible to improve coating film adhesion without impairing the mechanical properties of the resin molded body, as will be described later.
At least one of the polyamide components is preferably polyamide 6 or 6. By using at least one of polyamides 6 and 6, it becomes possible to suppress a decrease in heat resistance and the like.

（式中、Ｒ^１及びＲ^２は、それぞれ独立して、炭素数３〜１４のアルキレン基又は炭素数６〜９のアリーレン基である。但し、Ｒ^１及びＲ^２は同時に炭素数６のアルキレン基又は炭素数６のアリーレン基であることはない。）
これらの中でも、ポリアミド４，６、ポリアミド６，１２、ポリアミド６，６／６，Ｉ、ポリアミド６，６／６，Ｔ、ポリアミド６，６／６，Ｉ／６，Ｔ、ポリアミド９，Ｔ、ポリアミド１２，Ｔから選ばれる１種以上であることが好ましく、ポリアミド６，１２、ポリアミド６，６／６，Ｉ、ポリアミド６，６／６，Ｔから選ばれる１種以上がより好ましく、ポリアミド６，１２及び／又はポリアミド６，６／６，Ｉが最も好ましい。
ポリアミド（Ａ）として、ポリアミド６，６とポリアミド６，６以外のポリアミドとを組み合わせて用いる場合のこれらの比率は、適宜決定することができるが、好ましくは、ポリアミド（Ａ）の合計重量に対して、ポリアミド６，６が９９重量％〜３０重量％の範囲であることが好ましい。より好ましくは９０重量％〜４５重量％の範囲であり、最も好ましくは、８０重量％〜５０重量％の範囲内である。 As polyamides other than polyamide 6 and 6, polyamide 6 and / or polyamide represented by the following formula are preferable.

(Wherein R ¹ and R ² are each independently an alkylene group having 3 to 14 carbon atoms or an arylene group having 6 to 9 carbon atoms, provided that R ¹ and R ² are alkylene groups having 6 carbon atoms at the same time. Group or arylene group having 6 carbon atoms.)
Among these, polyamide 4,6, polyamide 6,12, polyamide 6,6 / 6, I, polyamide 6,6 / 6, T, polyamide 6,6 / 6, I / 6, T, polyamide 9, T, One or more selected from polyamide 12, T is preferable, and one or more selected from polyamide 6, 12, polyamide 6, 6/6, I, polyamide 6, 6/6, T is more preferable, polyamide 6 12 and / or polyamide 6,6 / 6, I are most preferred.
As the polyamide (A), these ratios in the case of using a combination of polyamide 6,6 and a polyamide other than polyamide 6,6 can be determined as appropriate, but preferably with respect to the total weight of the polyamide (A) Thus, the polyamide 6,6 is preferably in the range of 99% by weight to 30% by weight. More preferably, it is in the range of 90 wt% to 45 wt%, and most preferably in the range of 80 wt% to 50 wt%.

Moreover, it is preferable that the polyamide (A) which can be used for the resin molding of the present invention contains at least one polyamide having a terminal amino group concentration of 1 × 10 ⁵ to 4 × 10 ⁵ mol / kg. Furthermore, it is more preferable that the terminal amino group concentration includes at least one polyamide having a concentration of 2 × 10 ^{5 to} 3 × 10 ⁵ mol / kg. The terminal carboxyl group concentration at this time is not particularly limited, but is preferably at least 5 × 10 ⁵ mol / g or more. More preferably, it is 6 × 10 ^{5 to} 13 × 10 ⁵ mol / kg.
Adjustment of these end groups is sufficient if the end groups of at least one polyamide among the different polyamides used as the polyamide (A) are adjusted. Among these, it is desirable to control the polyamides 6 and 6.
As a method for adjusting the end groups of these polyamide resins, a known method that will be apparent to those skilled in the art can be used. For example, there may be mentioned a method of adding one or more selected from diamine compounds, monoamine compounds, dicarboxylic acid compounds, monocarboxylic acid compounds and the like so as to have a predetermined terminal concentration during polymerization of polyamide.

Further, in the resin molded body of the present invention, Japanese Patent Application Laid-Open No. 01-163262 (corresponding to US Pat. No. 4,857,575) known for the purpose of improving the heat resistance stability of the polyamide resin. Metal-based stabilizers as described can also be used without problems.
Among these metal stabilizers, those that can be particularly preferably used include CuI, CuCl ₂ , copper acetate, cerium stearate, and the like. Further, halogenated salts of alkyl metals typified by potassium iodide, potassium bromide and the like can also be suitably used. Of course, these may be added together.
A preferable blending amount of the metal stabilizer and / or the halogenated salt of the alkyl metal is 0.001 to 1 part by weight with respect to 100 parts by weight of the polyamide (A) as a total amount.

Moreover, in the resin molding of this invention, a well-known organic stabilizer other than the metal stabilizer mentioned above can be used without a problem. Examples of organic stabilizers include hindered phenol antioxidants typified by Irganox 1098, phosphorus processing heat stabilizers typified by Irgaphos 168, and lactone processing heat stability typified by HP-136. Agents, sulfur heat stabilizers, hindered amine light stabilizers, and the like.
Among these organic stabilizers, a hindered phenol antioxidant, a phosphorus processing heat stabilizer, or a combination thereof is more preferable. A preferable blending amount of these organic stabilizers is 0.001 to 1 part by weight with respect to 100 parts by weight of the polyamide (A).
In addition to the above, known additives that can be added to the polyamide may be added in an amount of less than 10 parts by weight based on 100 parts by weight of the polyamide (A).

〔式中、Ｏは酸素原子、Ｒは、それぞれ独立して、水素、ハロゲン、第一級もしくは第二級の炭素数１〜３の低級アルキル基、炭素数６〜９のアリール基、炭素数１〜３のハロアルキル基、炭素数１〜３のアミノアルキル基、炭素数１〜３の炭化水素オキシ基、又は炭素数１〜３のハロ炭化水素オキシ基（但し、少なくとも２個の炭素原子がハロゲン原子と酸素原子を隔てている）を表わす。〕 The polyphenylene ether that can be used in the resin molded product of the present invention is a homopolymer and / or copolymer composed of the structural units of the following formula.

[Wherein, O is an oxygen atom, R is independently hydrogen, halogen, primary or secondary lower alkyl group having 1 to 3 carbon atoms, aryl group having 6 to 9 carbon atoms, carbon number 1 to 3 haloalkyl groups, 1 to 3 aminoalkyl groups, 1 to 3 hydrocarbonoxy groups, or 1 to 3 halohydrocarbonoxy groups (provided that at least 2 carbon atoms Represents a halogen atom and an oxygen atom). ]

Specific examples of the polyphenylene ether (B) that can be used in the resin molded product of the present invention include, for example, poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl- 1,4-phenylene ether), poly (2-methyl-6-phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether), and the like. -Copolymers of dimethylphenol and other phenols (for example, copolymers with 2,3,6-trimethylphenol as described in JP-B-52-017808 (US Pat. No. 4,011,200)) And a polyphenylene ether copolymer such as a copolymer and a copolymer with 2-methyl-6-butylphenol).
Among these, particularly preferred polyphenylene ethers include poly (2,6-dimethyl-1,4-phenylene ether), a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, or these It is a mixture.

The manufacturing method of polyphenylene ether (B) used with the resin molding of this invention is not specifically limited, A well-known method can be used. For example, U.S. Pat. Nos. 3,306,874, 3,306,875, 3,257,357, and 3,257,358, and JP-A-50-051197 (corresponding to U.S. Pat. No. 3,929,930). And the production methods described in JP-B-52-015880 and JP-A-63-152628 (corresponding to US Pat. No. 4,011,200).
The reduced viscosity (η _{sp / c} : 0.5 g / dl, chloroform solution, measured at 30 ° C.) of the polyphenylene ether (B) that can be used in the resin molded product of the present invention is 0.15 to 0.70 dl / g. It is preferable that it is the range of 0.20-0.60 dl / g, More preferably, it is the range of 0.40-0.55 dl / g.

In addition, it is more useful to use two or more polyphenylene ethers having different reduced viscosities as the polyphenylene ether (B) because the balance between fluidity and impact resistance can be improved. For example, a combination of a polyphenylene ether having a reduced viscosity of 0.45 dl / g or less and a polyphenylene ether having a reduced viscosity of 0.50 dl / g or more, a polyphenylene ether having a reduced viscosity of 0.40 dl / g or less, and a reduced viscosity of 0.50 dl / g or more. A combination with polyphenylene ether and the like can be mentioned, but of course, the present invention is not limited to these.
Furthermore, it is preferable that at least one polyphenylene ether used as the polyphenylene ether (B) is a modified polyphenylene ether. In particular, it is preferable to use a combination of a modified polyphenylene ether and an unmodified polyphenylene ether as the polyphenylene ether (B).
The modified polyphenylene ether here means at least one carbon-carbon double bond or triple bond in the molecular structure, and at least one carboxylic acid group, acid anhydride group, amino group, hydroxyl group or glycidyl group. The polyphenylene ether modified with at least one modifying compound having the following formula can be used, and all the modified polyphenylene ethers described in International Publication No. WO02 / 094936 can be used.

The modified polyphenylene ether used in the production of the resin molded body of the present invention may be in the form of powder or pellet, but is preferably in the form of pellet.
In addition, when a modified polyphenylene ether and an unmodified polyphenylene ether are used in combination, the amount of the modified polyphenylene ether is not particularly limited, but preferably 10% relative to the total weight of the polyphenylene ether (B). It is -95 weight%, More preferably, it is 30-90 weight%, Most preferably, it is 45-85 weight%.
A preferable addition form of polyphenylene ether at the time of production of the resin molded body of the present invention is to add a part or all of polyphenylene ether in the form of pellets melt-kneaded in advance. By doing so, it is possible to improve biting into an extruder and the like, and it is possible to improve the production amount per hour during production. Furthermore, in general, when the production volume per hour is improved, the devolatilization efficiency during production decreases, and silver streaks on the molded piece when staying in the molding machine becomes a problem. By making the part or the whole into the shape of a pellet kneaded in advance, this silver streak can be suppressed and it is effective.

Moreover, it is preferable that polyphenylene ether (B) used for the resin molding of this invention has specific molecular weight distribution. Specifically, the polyphenylene ether (B) includes a relatively high molecular weight polyphenylene ether molecule having a molecular weight of 200,000 or more and a relatively low molecular weight polyphenylene ether molecule having a molecular weight of 5,000 or less. ) And / or (II).
(I) The weight ratio of the relatively high molecular weight polyphenylene ether molecule to the relatively low molecular weight polyphenylene ether molecule is 0.35 or less.
(II) The amount of the relatively low molecular weight polyphenylene ether molecule and the relatively high molecular weight polyphenylene ether molecule relative to the weight of the polyphenylene ether (B) is 5% by weight or less and 2% by weight or less, respectively.
It is more preferable to satisfy both the requirements (I) and (II). By controlling the molecular weight of the polyphenylene ether (B) so as to satisfy the requirements (I) and / or (II), the coating film adhesion can be further improved.

The above-described measurement of the amount of the relatively low molecular weight polyphenylene ether molecule and the relatively high molecular weight polyphenylene ether molecule can be performed by a method including the following steps 1) to 3).
1) Finely pulverize a molded body having an amount sufficient for measurement, soak it in chloroform, and dissolve the soluble component sufficiently with an ultrasonic cleaner or the like.
2) The obtained solution is measured using a gel permeation chromatography (GPC) measuring device and an ultraviolet spectroscopic detector, and molecular weight data converted with standard polystyrene is obtained.
3) The obtained molecular weight data is fractionated at a specific molecular weight using commercially available GPC processing software, and the amount is calculated. At this time, it is important to set the wavelength of ultraviolet rays to be measured to a wavelength at which the block copolymer does not absorb because the block copolymer eluting simultaneously is not detected.
[Measurement conditions GPC apparatus: GPC SYSTEM21: Showa Denko KK, detector: UV-41: Showa Denko KK, solvent: chloroform, temperature: 40 ° C, column: sample side (KG, K- 800RL, K-800R), reference side (K-805L × 2), flow rate 10 ml / min, measurement wavelength: 283 nm, pressure 15-17 kg / cm ² )]

Moreover, in the resin molding of this invention, you may mix | blend a styrene-type thermoplastic resin, if it is a quantity less than 50 weight part with respect to a total of 100 weight part of polyamide (A) and polyphenylene ether (B). .
The styrenic thermoplastic resin referred to here is polystyrene (homopolymer), rubber-modified polystyrene (HIPS), styrene-acrylonitrile copolymer (AS resin), styrene-rubber polymer-acrylonitrile copolymer (ABS resin). It is one or more chosen from.
Various stabilizers conventionally used for stabilizing the polyphenylene ether (B) can also be suitably used. Examples of stabilizers are metal stabilizers such as zinc oxide and zinc sulfide, organic stabilizers such as hindered phenol stabilizers, phosphorus stabilizers, and hindered amine stabilizers. The amount is less than 5 parts by weight based on 100 parts by weight of the polyphenylene ether (B).
Further, known additives conventionally used for polyphenylene ether may be added in an amount of less than 10 parts by weight based on 100 parts by weight of polyphenylene ether (B).

Next, the partially hydrogenated block copolymer (C) that can be used in the resin molded product of the present invention will be specifically described.
The partially hydrogenated block copolymer (C) that can be used in the resin molding of the present invention is at least one aromatic vinyl polymer block mainly composed of an aromatic vinyl monomer unit and a conjugated diene monomer. It is obtained by partially hydrogenating a non-hydrogenated block copolymer comprising at least one conjugated diene polymer block mainly composed of a body unit.
The partially hydrogenated block copolymer (C) includes at least one partially hydrogenated block copolymer (C-1) having a number average molecular weight of 200,000 to 300,000.
Regarding the above aromatic vinyl polymer block, “mainly composed of an aromatic vinyl monomer unit” refers to a block in which at least 50% by weight or more is an aromatic vinyl monomer unit. More preferably, the aromatic vinyl monomer unit is 70% by weight or more, more preferably 80% by weight or more, and most preferably 90% by weight or more.

The same applies to “consisting mainly of a conjugated diene monomer unit” and refers to a block in which at least 50% by weight or more is a conjugated diene monomer unit. More preferably, the conjugated diene monomer unit is 70% by weight or more, more preferably 80% by weight or more, and most preferably 90% by weight or more.
Further, the aromatic vinyl polymer block may be a copolymer block in which a small amount of a conjugated diene compound is randomly bonded to the aromatic vinyl polymer block, for example. Similarly, in the case of the conjugated diene polymer block, for example, a copolymer block in which a small amount of an aromatic vinyl compound is randomly bonded in the conjugated diene polymer block may be used.
Specific examples of the aromatic vinyl compound used for forming the aromatic vinyl monomer unit include styrene, α-methylstyrene, vinyltoluene and the like, and one or more compounds selected from these are used. Of these, styrene is particularly preferable.

Specific examples of the conjugated diene compound used for forming the conjugated diene polymer block include butadiene, isoprene, piperylene, 1,3-pentadiene, and one or more compounds selected from these are used. Of these, butadiene, isoprene and combinations thereof are preferred.
The microstructure of the conjugated diene polymer block portion of the partially hydrogenated block copolymer (C) is 1,2-vinyl content or the total amount of 1,2-vinyl content and 3,4-vinyl content is 5-80. %, More preferably 10 to 50%, and most preferably 15 to 40%.
The non-hydrogenated block copolymer used for the production of the partially hydrogenated block copolymer (C) includes an aromatic vinyl polymer block (a) and a conjugated diene polymer block (b), ab type, a A block copolymer having a bond type selected from the -ba type and the abbab type is preferred. Of these, block copolymers having different bond types may be used in combination. Among these, the aba type and the abbab type are more preferable, and the abba type is most preferable.

Further, the block copolymer used in the resin molded product of the present invention needs to be a partially hydrogenated block copolymer (partially hydrogenated block copolymer).
The partially hydrogenated block copolymer is a hydrogenation treatment of the above-mentioned non-hydrogenated block copolymer so that the aliphatic double bond of the conjugated diene polymer block is in the range of more than 0 and less than 100%. Controlled thing. A preferable hydrogenation rate of the partially hydrogenated block copolymer is 50% or more and less than 100%, more preferably 80% or more and less than 100%, and most preferably 98% or more and less than 100%.
Furthermore, the partially hydrogenated block copolymer used in the resin molded product of the present invention needs to contain a partially hydrogenated block copolymer (C-1) having a number average molecular weight of 200,000 or more and 300,000 or less. There is. When only a partially hydrogenated block copolymer having a number average molecular weight of less than 200,000 is used, the coating film adhesion decreases, and when only a partially hydrogenated block copolymer having a number average molecular weight exceeding 300,000 is used, the resin of the present invention. Since the fluidity | liquidity of the composition used when manufacturing a molded object falls, it is not preferable.

Here, the number average molecular weight is measured with an ultraviolet spectroscopic detector [UV-41: Showa Denko KK] using a gel permeation chromatography measuring apparatus [GPC SYSTEM21: Showa Denko KK]. This refers to the number average molecular weight in terms of standard polystyrene.
[Measurement conditions Solvent: Chloroform, Temperature: 40 ° C., Column: Sample side (KG, K-800RL, K-800R), Reference side (K-805L × 2), Flow rate 10 ml / min, Measurement wavelength: 254 nm , Pressure 15-17 kg / cm ² )]
At this time, a low molecular weight component due to catalyst deactivation during polymerization may be detected. In this case, the low molecular weight component is not included in the molecular weight calculation. Usually, the calculated correct molecular weight distribution (weight average molecular weight / number average molecular weight) is in the range of 1.0 to 1.1.
Moreover, in the resin molding of this invention, the said partial hydrogenated block copolymer (C) is this at least 1 partial hydrogenated block copolymer (C-) whose number average molecular weight is 200,000-300,000. 1) can be used in combination with at least one partially hydrogenated block copolymer (C-2) having a number average molecular weight of 50,000 to 150,000. As described above, by using the partially hydrogenated block copolymers (C-1) and (C-2) in combination, it is possible to improve the coating film adhesion and the balance between impact resistance and fluidity.

As the partially hydrogenated block copolymer (C), the at least one partially hydrogenated block copolymer (C-1) and the at least one partially hydrogenated block copolymer (C-2) are combined. When used, the partially hydrogenated block copolymers (C-1) and (C-2) as a whole
A highly aromatic vinyl content partially hydrogenated block copolymer obtained by partially hydrogenating a non-hydrogenated block copolymer having a content of the aromatic vinyl polymer block of 60 wt% to 90 wt%, And a low aromatic vinyl content partially hydrogenated block copolymer obtained by partially hydrogenating a non-hydrogenated block copolymer having a content of the aromatic vinyl polymer block of less than 20% by weight to less than 60% by weight. Including coalescence,
The total amount of the aromatic vinyl polymer block present in the partially hydrogenated block copolymers (C-1) and (C-2) is the amount of the partially hydrogenated block copolymers (C-1) and (C-2). ) Is preferably 30 to 40% by weight based on the total weight.

By combining the high aromatic vinyl content partially hydrogenated block copolymer and the low aromatic vinyl content partially hydrogenated block copolymer, it is possible to achieve both impact resistance and high temperature rigidity. It becomes.
In that case, a high aromatic vinyl content partially hydrogenated block copolymer obtained by partially hydrogenating a non-hydrogenated block copolymer having a content of the aromatic vinyl polymer block of 60% by weight to 90% by weight. It is particularly preferable to use a copolymer which is a partially hydrogenated block copolymer (C-2) (number average molecular weight 50,000 to 150,000).
In addition, as a measure of the number average molecular weight of the partially hydrogenated block copolymer and the content of the aromatic vinyl polymer block at this time, the number average molecular weight of the aromatic vinyl polymer block should be 20,000 or more. It is more preferable to select a block copolymer having an appropriate number average molecular weight and an aromatic vinyl polymer block content.

The number average molecular weight of the aromatic vinyl polymer block can be obtained by the following formula using the number average molecular weight of the block copolymer described above.
Mn _(a) = {Mn × a / (a + b)} / N
[In the above formula, Mn _(a) is the number average molecular weight of the aromatic vinyl polymer block, Mn is the number average molecular weight of the block copolymer, and a is the number of all aromatic vinyl polymer blocks in the block copolymer. % By weight, b is the weight% of all conjugated diene polymer blocks in the block copolymer, and N is the number of aromatic vinyl polymer blocks in the block copolymer. ]
The above partially hydrogenated block copolymers have different bond types, different aromatic vinyl compound types, different conjugated diene compound types, and 1,2-bonded vinyl unless otherwise contrary to the spirit of the present invention. A mixture of those having different amounts or 1,2-bonded vinyl contents and 3,4-bonded vinyl contents, those having different aromatic vinyl monomer unit contents, or those having different hydrogenation rates may be used. Absent.

In addition, said non-hydrogenated block copolymer can be manufactured by a well-known method. Moreover, partial hydrogenation of said non-hydrogenated block copolymer can also be performed by a well-known method.
In the present invention, a block copolymer modified in whole or in part, or a block copolymer preliminarily mixed with oil, as described in International Publication WO02 / 094936, is also suitable. Can be used.
Furthermore, the resin molded body of the present invention may contain a carbon material (D). By adding the carbon material (D), it can be applied to uses that require electrical conductivity.
The carbon material (D) that can be used in the resin molded body of the present invention is a carbon-based filler that can be improved in conductivity (lowered volume resistivity) by being added.

  Among the carbon materials, conductive carbon black, carbon fibrils, carbon nanotubes, or a mixture thereof can be preferably used. Examples of the conductive carbon black that can be used in the present invention include carbon black described in WO 01/081473 as conductive carbon black. Examples of commercially available conductive carbon blacks include Ketjen Black EC and Ketjen Black EC600JD available from Ketjen Black International. Moreover, as a carbon fibril which can be used by this invention, the fine carbon fiber etc. which are described in the international publication patent WO94 / 023433 are mentioned. Carbon fibrils also include carbon nanotubes in a broad sense, but a tubular carbon material having a specific structure is called a carbon nanotube. In the present invention, the carbon nanotube means US Pat. No. 4,663,230, US Pat. No. 4,663,230, US Pat. No. 5,165,909, US Pat. No. 5,171,560, US Pat. No. 5,578,543, US Pat. This refers to a carbon fiber having less branching and having a hollow structure with a fiber diameter of less than 75 nm as described in US Pat. No. 5,589,152, US Pat. No. 5,650,370, US Pat. No. 6,235,674 and the like. Moreover, the thing of the coil shape which a helix makes a round with the pitch of 1 micrometer or less is also contained. The structure of the carbon nanotube in the present invention may be a single layer or a multilayer. Further, carbon fibers having a relatively branched structure and a fiber diameter of 75 nm or more and having a hollow structure are also included. Examples of commercially available carbon nanotubes include BN fibrils available from US Hyperion Catalyst International.

A preferable addition amount of these carbon materials (D) in the resin molded body of the present invention is 0.5 to 2.5% by weight with respect to the weight of the resin molded body. More preferably, it is 1.0 to 2.0% by weight.
As a preferable addition method of the carbon material (D) used in the present invention, at least a part of the carbon material (D) is added to the polyamide (A), the polyphenylene ether (B), and the partially hydrogenated block copolymer. It is a method for producing a resin molded body using a master batch dispersed in at least a part of at least one selected from (C). More preferably, it is a method using a master batch in which at least a part of the carbon material (D) is dispersed in at least a part of the polyamide (A). Although there is no restriction | limiting in particular in the manufacturing method of a masterbatch, Melt kneading using an extruder is the most preferable. More preferably, after supplying a resin such as polyamide (A) from the upstream supply port and melt-kneading using a co-rotating twin screw extruder having two or more supply ports set at 250 to 300 ° C. And a method of supplying the carbon material (D) from the downstream supply port and melt-kneading. At this time, the resin temperature is more preferably less than 340 ° C. A preferable blending amount of the carbon material (D) in the master batch is 5 to 30% by weight. More preferably, it is 8 to 25% by weight.

At least a part of the carbon material (D) is not particularly limited in the form of a master batch, and examples thereof include powder, pellets, sheets, strands, and irregular lumps. It is preferable that it is a shape.
A commercially available master batch may be used. Examples of commercially available master batches include polyamide 66 / carbon fibril master batch (trade name: Polyamide 66 with Fiber Nanotubes RMB 4620-00: carbon fibril amount 20 wt%) available from US Hyperion Catalyst International. .
You may mix | blend a wollastonite particle (E) with the resin molding of this invention. Preferable wollastonite particles (E) have an average particle size in the range of 2 to 9 μm and an aspect ratio of 5 or more. [The average particle size here is a model of Sedigraph particle size analyzer (manufactured by Micromeritics Instruments, USA) 5100), 0.75 g of wollastonite particles were added to 45 ml of 0.05% Calgon solution, sufficiently dispersed in an ultrasonic bath, measured, and the calculated equivalent spherical diameter was shown. The aspect ratio was The diameter and length of at least 5000 wollastonite particles are measured using a photograph observed and photographed with a scanning electron microscope, and a value calculated from an average value of the measured values is shown.

Furthermore, it is more preferable to use two or more types of wollastonite particles having different aspect ratios in combination. Specifically, for example, it is preferable to use a combination of wollastonite particles having an aspect ratio of 5 or more and wollastonite particles having an aspect ratio of less than 5. In that case, it is most preferable to use 50% by weight or more of wollastonite particles having an aspect ratio of 5 or more with respect to the total weight of all wollastonite particles (E).
As a preferred method for adding the wollastonite particles (E) when producing the resin molded body of the present invention, the wollastonite particles (E) are added to other materials together with the polyphenylene ether (B) and kneaded, A method of obtaining a resin molded body, a method of adding a wollastonite particle (E) together with the polyamide (A) to other materials and kneading them to obtain a resin molded body, melting a polyphenylene ether (B) and a polyamide (A) Examples thereof include a method of adding a wollastonite particle (E) after kneading and further melt-kneading to obtain a resin molded body. Among these, polyphenylene ether (B) and polyamide (A ) Is melt kneaded, followed by addition of wollastonite (E) and further melt kneading.
Further, these wollastonite particles (E) are prepared in advance in order to improve the dispersibility and handling of the wollastonite particles (E), and at least a part of the polyamide (A) and / or a partially hydrogenated block copolymer. It can be added in the form of a wollastonite-containing masterbatch obtained by dispersing it in a small part.

As a detailed production method of the wollastonite-containing masterbatch, for example, (1) a method of polymerizing raw material monomers in the presence of wollastonite during the production of polyamide (A),
(2) Using an extruder, polyamide (A) and / or partially hydrogenated block copolymer (C) and wollastonite are dry blended to obtain polyamide (A) and / or partially hydrogenated block copolymer. (C) A method of kneading in a temperature range that is sufficient for melting and hardly causing thermal decomposition, and (3) an upstream supply using a twin-screw extruder having an upstream supply port and a downstream supply port Examples thereof include a method of supplying the polyamide (A) and / or the partially hydrogenated block copolymer (C) from the mouth, and adding wollastonite from the downstream feed port. Among these, the method (3) is more preferable.
You may add a compatibilizing agent at the time of manufacture of the resin molding of this invention.
The compatibilizing agent that can be used is not particularly limited as long as it improves the physical properties of the polyamide-polyphenylene ether mixture. Specifically, the compatibilizing agent refers to a polyfunctional compound that interacts with polyphenylene ether, polyamide, or both. This interaction may be chemical (eg, grafting) or physical (eg, changing the surface properties of the dispersed phase).

Examples of compatibilizers that can be used in the production of the resin molded body of the present invention include Japanese Patent Application Laid-Open No. 08-008869 (corresponding to European Patent Publication No. 201416) and Japanese Patent Application Laid-Open No. 09-124926 ( And the like, and all of these known compatibilizers can be used and can be used in combination.
Among these various compatibilizing agents, examples of particularly suitable compatibilizing agents include maleic anhydride or derivatives thereof, maleic acid or derivatives thereof, citric acid or derivatives thereof, fumaric acid or derivatives thereof, and Examples include modified polyphenylene ether pellets.
A preferable amount of the compatibilizer is 0.01 to 25 parts by weight based on 100 parts by weight of the total of the polyamide (A) and the polyphenylene ether (B).
Although there is no restriction | limiting in particular in the preferable form of the compatibilizing agent which can be used in this invention, since the particle shape is excellent in handling property rather than powder shape, it is preferable. Specifically, when using a compatibilizing agent with an irritating odor such as maleic anhydride, the granular form is more preferable than the powder form because the odor is reduced and the working environment is hardly deteriorated.
The preferred particle size of these granular compatibilizers is 1 mm or more in diameter. More preferably, it has a granular form with a diameter of 1 mm to 10 mm. Most preferred is a granular shape having a diameter of 3 to 8 mm. If the diameter is 10 mm or less, there is no possibility of problems in supplying to the extruder.

In the resin molding of the present invention, the polyamide (A) forms a continuous phase, the polyphenylene ether (B) is dispersed in the continuous phase to form a dispersed phase, and the partially hydrogenated block copolymer Is present in at least one phase selected from the group consisting of the continuous phase of the polyamide (A) and the dispersed phase of the polyphenylene ether (B). In a composition region in which polyamide cannot form a continuous phase, coating film adhesion deteriorates rapidly. In this case, there is no particular limitation on the dispersion state of the block copolymer in the dispersed phase, and even if the microphase separation structure as shown in US Pat. It may be a structure in which the coalescence is present as a lump.
In the resin molded body of the present invention, the polyamide (A) is exposed on the surface of the molded body, and the total area of the polyamide (A) exposed on the surface of the molded body is the surface area of the molded body. Must be 80% or more. Further, the total area of the polyamide (A) (hereinafter often simply referred to as “polyamide area ratio”) is preferably 90% or more.
When the polyamide area ratio is less than 80%, the coating film adhesion is significantly lowered.

The polyamide area ratio on the surface of the molded body here can be measured by the following method.
The molded body is cut into a shape having a width of about 1 cm and a length of about 1 cm (in the case of pellets, it is used as it is without being cut), and a 10% by weight aqueous solution of phosphorus-tungstic acid adjusted to 20 to 80 ° C. And soaking in a range not exceeding 24 hours to selectively dye the polyamide part.
After dyeing, the molded product is taken out, washed with water and dried, and the surface of the obtained flat plate-shaped molded piece is used with a field emission scanning electron microscope FE-SEM [device name: S-4700 type / manufactured by Hitachi, Ltd.]. A backscattered electron image is taken at an angle perpendicular to the surface under an acceleration voltage of 5 kV. (Magnification is 2,500 times)
At this time, the polyamide dyed on tungsten appears white due to the electron reflection of tungsten, and the other undyed parts appear black, and the surface polyamide can be discriminated.
The ratio of the area reflected in white with respect to the total area of the obtained reflection electron image photograph was calculated by using an image analysis apparatus (device name: Image-Pro PLUS ver. 4.0 / manufactured by Media Cybernetics, USA), and polyamide. The area ratio. (At this time, as the binarization threshold when calculating the area ratio of white and black, the peak value of white and black is obtained from the histogram of the color tone, and the intermediate value is used.)

When the polyamide area ratio on the surface of the molded body is measured, at least 10 sites are observed, and the average value of the values calculated at each site is expressed. Further, in that case, a location where the amount of polyamide is expected to be lower than other locations as judged from the structure of the molded product and the manufacturing method of the molded product (for example, flow during injection molding) Measure not at the end) but at 10 different places near the center of the compact. (For example, when a molded body is manufactured by injection molding, when the gate portion is 0 and the distance from the gate portion to the flow end portion is 1, measurement is performed at a location at a distance of 0 to 0.8 from the gate portion. )
In addition, when the resin molded body of the present invention is a strand cut pellet (a pellet that is cooled in a water bath and then cut into strands after leaving the extruder), the cut surface is not included in the area, and the measurement site Also do it other than on the cut surface.
In the present invention, in order to achieve excellent coating film adhesion of the resin molded body, it is essential that the surface area of the polyamide is high, but the coating film adhesion is more than that of polyamide alone and polyphenylene ether alone. Also has the feature of being excellent.

The resin molded body of the present invention causes moderate irregularities in a form in which the dispersed phase resin (polyphenylene ether (B) and partially hydrogenated block copolymer (C)) is raised on the surface of the molded body, and the irregularities are formed on polyamide ( A) exhibits an effect by coating. In order to cause moderate unevenness on the surface of the molded body by the dispersed phase resin, it is necessary to increase the melt viscosity of the dispersed phase. Further, in order to obtain a good coating of the dispersed phase with the polyamide (A), it is desirable to set the melt viscosity of the polyamide (A) low.
In order to sufficiently increase the melt viscosity of the dispersed phase resin and cause appropriate irregularities on the surface of the molded body, it is necessary to control the molecular weight of the partially hydrogenated block copolymer (C) to be high. Specifically, by using the partially hydrogenated block copolymer (C-1) having a number average molecular weight of 200,000 to 300,000, appropriate irregularities can be produced on the surface of the molded body.
When a polyamide having a low melt viscosity is used alone as the polyamide (A), the polyamide area ratio can be set high, but a phenomenon in which mechanical properties (impact strength, etc.) are reduced occurs. In addition, when a polyamide having a high melt viscosity is used alone, the mechanical properties are improved, but the polyamide area ratio on the surface of the molded body is lowered, and the coating film adhesion is lowered. In order to achieve both, it is necessary to use two or more kinds of polyamides as described above.

In the present invention, the melt viscosity (290 ° C., 1000 sec ⁻¹ ) of the resin (polyphenylene ether (B) and partially hydrogenated block copolymer (C)) forming the dispersed phase is preferably 800 Pa · sec or more. . More preferably, it is 1000 Pa · sec or more.
The melt viscosity (290 ° C., 1000 sec ⁻¹ ) of the resin (polyamide (A)) forming the continuous phase is preferably less than 200 Pa · sec. More preferably, it is less than 100 Pa · sec.
Further, the ratio of the melt viscosity of the dispersed phase resin to the continuous phase resin (ratio of the melt viscosity of the resin forming the dispersed phase to the melt viscosity of the resin forming the continuous phase) is preferably 10 or more, more preferably 20 That's it.
For example, in the case of a dispersed phase resin, the melt viscosity of the dispersed phase resin and the continuous phase resin is extruded only with the resin composition forming the dispersed phase, and the melt viscosity of the obtained pellet is measured with a capillary rheometer or the like. It is measurable by doing. The same applies to the continuous phase resin.
However, when an additive such as wollastonite is used as a component of the resin molding, the measurement is performed without including these.
The melt viscosity of the resin forming the dispersed phase is 800 Pa · s or more, the melt viscosity of the resin forming the continuous phase is less than 200 Pa · s, and the melt viscosity ratio of the dispersed phase resin and the continuous phase resin is 10 or more. Thus, it becomes easy to improve the polyamide area ratio and to keep the high coating film adhesion characteristic of the resin molded body of the present invention high.

  In the present invention, a range in which the weight ratio of the dispersed phase to the continuous phase is less than 1.0 is preferable. More preferably, it is 0.9 or less. By setting the composition ratio to less than 1.0, the polyamide area ratio can be stably increased. When the partially hydrogenated block copolymer (C) is present in the dispersed phase of the polyphenylene ether (B), the ratio of the polyphenylene ether (B) in the dispersed phase is based on the weight of the entire dispersed phase. And 50 to 90% by weight is preferable. By keeping the polyphenylene ether concentration in the dispersed phase high, the gloss rate can be kept low. Specifically, the polyamide (A) is 50 to 70% by weight and the polyphenylene ether (B) is based on the total weight of the polyamide (A), the polyphenylene ether (B), and the partially hydrogenated block copolymer (C). It is preferably 25 to 45% by weight, and the partially hydrogenated block copolymer (C) is preferably in the range of 5 to 25% by weight. More preferably, the polyamide (A) is 50 to 60% by weight, the polyphenylene ether (B) is 35 to 45% by weight, and the partially hydrogenated block copolymer (C) is 5 to 15% by weight.

The resin molded body of the present invention is said that the polyamide area ratio on the surface of the molded body exceeds 80% even if the polyamide blending amount is less than 80% by weight (the polyamide ratio in the surface is different from the polyamide ratio in the bulk). However, there is a feature, and thereby the coating film adhesion can be expressed.
In the resin molded product of the present invention, examples of the method for setting the polyamide area ratio to 80% or more include a method of setting the viscosity at the time of melting of the continuous phase resin lower than that of the dispersed phase resin, polyamide (A) and polyphenylene ether For example, the amount of the reaction product (graft) produced in (B) is controlled to an appropriate amount.
As a specific method for setting the viscosity at the time of melting of the continuous phase resin lower than that of the dispersed phase resin, the method of adjusting the viscosity of the polyamide (A) as described above, the molecular weight of the polyphenylene ether in the molded body However, a method of adjusting the degree of polymerization of polyphenylene ether so as to be in the preferred range below, a method of blending two or more kinds of polyphenylene ethers having different molecular weights, and the like can be mentioned.

In addition, as a method for controlling the amount of reaction product generated between the polyamide (A) and the polyphenylene ether (B) to an appropriate amount, a method of selecting a polyamide having an amino group concentration in the specific range described above, Examples of the method include adjustment (for example, a method of preparing a mixture of a modified polyphenylene ether and an unmodified polyphenylene ether).
The method for setting the polyamide area ratio to 80% or more is not limited to the above-described method, and a plurality of methods may be used as a matter of course.
Further, in the resin molded body of the present invention, the preferred blending amount when using wollastonite is the average linear expansion coefficient of the molded body [melting temperature of 290 ° C. under the molding conditions specified in ISO 15103-2: 1997, mold A center part of a type D2 flat plate having a thickness of 2 mm as defined in ISO 294-3: 1996 molded at a temperature of 90 ° C. is cut to 10 mm (resin flow direction) × 3 mm (flow perpendicular direction) × 2 mm (thickness direction), 100 Measured at a rate of temperature increase of 5 ° C./min in a temperature range of −30 to 80 ° C. according to JIS K7197-1991 using a test piece left in a state of 48 hours or more in an environment of ° C.] is 4.5 × 10 ^−5. ° C. it is desirable that an amount falling in the range of ^{-1 ~6.5} × ^{10 -5} ℃ ^-1.
Specifically, the amount is preferably 10 to 50 parts by weight with respect to the total weight of the polyamide (A), polyphenylene ether (B), and partially hydrogenated block copolymer (C). More preferably, it is 15 to 35 parts by weight.

In the present invention, in addition to the above-described components, additional components may be added as necessary within a range that does not impair the effects of this component.
Examples of additional components include other thermoplastic resins such as polyester and polyolefin, inorganic fillers (talc, kaolin, zonotlite, titanium oxide, potassium titanate, carbon fibers, glass fibers, etc.), inorganic fillers and resins Known silane coupling agents, flame retardants (halogenated resins, silicone flame retardants, magnesium hydroxide, aluminum hydroxide, organic phosphate compounds, ammonium polyphosphate, red phosphorus, etc.) , Fluorinated polymers showing anti-drip effect, plasticizers (oil, low molecular weight polyolefin, polyethylene glycol, fatty acid esters, etc.), flame retardant aids such as antimony trioxide, colorants such as carbon black, carbon fibers, conductive Conductivity imparting materials such as conductive carbon black and carbon fibril, antistatic Various peroxides, antioxidants, ultraviolet absorbers, a light stabilizer and the like.
The specific addition amount of these components is 100 weight in total with respect to 100 weight parts of the total amount of polyamide (A), polyphenylene ether (B), partially hydrogenated block copolymer (A) and compatibilizer. The range does not exceed the part.

The method for producing a resin composition used for producing the resin molded product of the present invention will be described below.
Specific processing machines for producing the resin composition include, for example, a single screw extruder, a twin screw extruder, a roll, a kneader, a Brabender plastograph, a Banbury mixer, etc. In particular, a twin-screw extruder having an upstream supply port and one or more downstream supply ports is most preferable.
In particular, it is most preferable to use a extruder having a screw diameter of 50 mm or more provided with three or more supply devices, and supply polyamide, polyphenylene ether, and compatibilizer to the extruders from different supply devices and melt knead them.
In particular, when a granular compatibilizer and powdered polyphenylene ether are used, classification is prevented by supplying them with different supply devices, and the ratio of the polyphenylene ether and the compatibilizer varies depending on the location in the supply device. This can prevent the problem.
If the ratio of polyphenylene ether and compatibilizer supplied to an extruder changes, the viscosity and particle size of the dispersed phase will change, and adverse effects such as changes in glossiness and coating film adhesion may occur depending on the location. There is.
In particular, it is preferable to use a screw-type weight feeder as a compatibilizer supply device. Use of a screw-type weight feeder increases the stability of the supply, which leads to stabilization of quality and is more effective.
The melt-kneading temperature at the time of processing is not particularly limited, but considering the kneading state and the like, the conditions under which a suitable composition is usually obtained can be arbitrarily selected from 240 to 360 ° C. The preferable resin temperature in this case is 310-340 degreeC.

Although the specific manufacturing method of said resin composition is illustrated below, of course, it is not limited to this.
One screw-type weight feeder and one belt-type weight feeder are arranged in the upstream supply port of a twin-screw extruder equipped with an upstream supply port and one or more downstream supply ports, and a screw is connected to the downstream supply port. 1 type weight feeder is arranged, (1) A mixture of block copolymer and polyphenylene ether is supplied from the belt type weight feeder, and the compatibilizer is independently supplied to the upstream supply port from the screw type weight feeder. After melt-kneading, supplying polyamide from the downstream supply port and melt-kneading, (2) supplying polyphenylene ether from the belt-type weight feeder, and independently mixing the compatibilizer and block copolymer mixture from the screw-type weight feeder And then supplying the polyamide to the upstream supply port, melt-kneading, then supplying the polyamide from the downstream supply port, and melt-kneading (3 Powdered polyphenylene ether is supplied from a belt-type weight feeder, and a compatibilizer and polyphenylene ether pellets are independently supplied to the upstream supply port from the screw-type weight feeder, melt-kneaded, and then polyamide is supplied from the downstream supply port. Examples thereof include a method of supplying and melt-kneading.
The resin composition thus obtained is molded by an arbitrary method to obtain the resin molded body of the present invention. The resin molded body as used in the present invention is not limited to those molded by injection molding, but includes extruded sheets, films, pellets, and injection molded bodies that are secondarily processed by injection molding or the like. A preferable resin molded body is a cylindrical pellet having a diameter of less than 3 mm and a length of less than 3 mm, a spherical pellet having a diameter of less than 3 mm, a disk-shaped pellet having a diameter of less than 4 mm, or an injection-molded body formed by injection molding these pellets.

In the second aspect of the present invention,
Polyamide (A),
Polyphenylene ether (B),
A block copolymer (C) comprising at least one aromatic vinyl polymer block mainly comprising an aromatic vinyl monomer unit and at least one conjugated diene polymer block mainly comprising a conjugated diene monomer unit;
Conductive carbon material (D) and wollastonite particles (E)
There is provided a conductive resin composition comprising:
As said polyamide (A) used in the conductive resin composition of this invention, the thing similar to what was mentioned above in relation to the resin molding of this invention can be used. However, in the conductive resin composition of the present invention, it is not necessary to use two or more different polyamide components, and only one type of polyamide may be used. However, it is preferable to use two or more different polyamide components as in the case of the resin molding of the present invention.

Regarding the polyphenylene ether (B) used in the conductive resin composition of the present invention, those similar to those described above in relation to the resin molded product of the present invention can be used.
The block copolymer (C) may be the same as that described above in relation to the resin molded product of the present invention, but may or may not be hydrogenated.
The block copolymer (C) used in the conductive resin composition of the present invention preferably has a number average molecular weight of 50,000 or more and less than 150,000.
Furthermore, regarding the conductive carbon material (D) and the wollastonite particles (E), the same materials as those described above in relation to the resin molded product of the present invention can be used.
Moreover, regarding the manufacturing method of the conductive resin composition of this invention, the manufacturing method of the resin composition used for manufacture of the above-mentioned resin molding of this invention can be used.

Applications of the molded article obtained by molding the resin molded article of the present invention and the conductive resin composition of the present invention include, for example, electric parts for motorcycles and automobiles represented by relay block materials, etc .; IC trays, various disc players Electrical and electronic parts such as chassis, cabinets, etc .; OA parts and machine parts such as various computers and peripheral equipment; motorcycle cowls, automobile bumpers, fenders, door panels, various malls, emblems, outer door handles It can be suitably used for exterior parts typified by door mirror housings, wheel caps, roof rails and their stay materials, spoilers, interior members typified by instrument panels, console boxes, trims, and the like.
Among these, it can be suitably used as an automobile exterior part.

EXAMPLES Hereinafter, although this invention is demonstrated more concretely using an Example and a comparative example, this invention is not limited at all by an Example.
[Production Example 1] Production of maleic anhydride-modified polyphenylene ether [hereinafter simply abbreviated as MPPE] 100 parts by weight of polyphenylene ether having a reduced viscosity of 0.42 dl / g was dry blended with 3 parts by weight of maleic anhydride, and ZSK-40 extruded. Pellets obtained by melt kneading at a resin temperature of 320 ° C. using a machine [manufactured by Coperion (Germany), L / D = 42].

[Production Example 2] Production of polyamide 6,6 / 6, I copolymer [hereinafter simply abbreviated as PA66 / 6I] 20.0 kg of equimolar salt of adipic acid and hexamethylenediamine, isophthalic acid and hexamethylenediamine, etc. Mole salt (5.0 kg), adipic acid (1.0 kg) and pure water (25 kg) were charged into a 50 L autoclave and stirred well. After sufficiently purging with nitrogen, the temperature was raised from room temperature to 220 ° C. over about 1 hour with stirring.
Under the present circumstances, although the internal pressure became 18 kg / cm < ² > -G by the natural pressure by the water vapor | steam in an autoclave, it continued further heating, removing water out of a reaction system so that it might not become a pressure more than 18 kg / cm < ² > -G. When the internal temperature reached 260 ° C. after 2 hours, the heating was stopped, the autoclave discharge valve was closed, and the system was cooled to room temperature over about 8 hours. After cooling, the autoclave was opened, and about 20 kg of polymer was taken out and ground.
The obtained pulverized polymer was subjected to solid phase polymerization at 200 ° C. for 10 hours under a nitrogen stream.
The polyamide obtained by solid phase polymerization contains about 19 mol% of hexamethylene isophthalamide units, the terminal amino group concentration is 3.9 × 10 ⁵ mol / g per kg of polymer, and the terminal carboxyl group concentration is 10.2. × 10 ⁵ mol / g.

[Production Example 3] Manufacture of polyamide / carbon master batch [hereinafter simply referred to as PA-MB] L / D having one supply port on the upstream side of the extruder and one port on the downstream side (of the screw length L of the extruder) Using a twin-screw extruder (ratio to screw diameter D) of 46 [ZSK-58MC: manufactured by Coperion (Germany)], the cylinder temperature from the upstream supply port to the downstream supply port is 280 ° C., downstream supply The temperature from the mouth to the die was set to 300 ° C., 90 parts by weight of PA66-1 was supplied from the upstream supply port, and 10 parts by weight of KB was supplied from the downstream supply port. At this time, the screw rotation speed was 400 rotations, and the discharge amount was 300 kg / h.

[ Reference Example 1 ]
ZSK70MC co-rotating twin screw extruder having one supply port on the upstream supply port and two supply ports on the downstream side [manufactured by Coperion, Germany, L / D = 46, first to twelfth 12 individually Cylinder unit capable of temperature setting, die, upstream supply port in first cylinder unit, downstream first supply port in sixth cylinder unit, second downstream in eighth cylinder unit A belt-type weight feeder and two screw-type weight feeders are arranged at the upstream supply port of the 5th cylinder unit and the 11th cylinder unit having a vent port capable of suction under reduced pressure. One screw type weight feeder was arranged at the first supply port.

Screw-type weight feeder (hereinafter simply referred to as feeder) having a reduced viscosity (0.5 g / dl, chloroform solution, 30 ° C.) having a polyphenylene ether powder [hereinafter simply abbreviated as PPE1] of 0.52 dl / g disposed at the upstream supply port Screw-type weight feeder supplied with maleic anhydride [manufactured by Mitsubishi Chemical Corporation: tablet shape with a diameter of 4 to 5 mm] (hereinafter simply referred to as MAH) as the compatibilizer. (Hereinafter simply abbreviated as “Feeder 2”), polystyrene-polyethylene butylene-polystyrene block copolymer having a number average molecular weight (Mn) of 246,000 (styrene content of 33%) [hereinafter simply abbreviated as “SEBS1”] 4 weight Part and number average molecular weight (Mn) 98,500 polystyrene-polyethylene butylene-polystyrene Lock copolymer (styrene content 29%) [hereinafter simply abbreviated as SEBS2] 8 parts by weight of a dry weight blended with a Henschel mixer, a belt-type weight feeder (hereinafter simply referred to as feeder 3) (Abbreviation). Further, from a screw-type weight feeder (hereinafter simply abbreviated as “feeder 4”) disposed at the downstream supply port, a viscosity number of 120 ml / g, a terminal amino group concentration of 2.5 × 10 ⁵ mol / g, and a terminal carboxyl group concentration of 11. 6 × 10 ⁵ mol / g polyamide 6,6 [hereinafter simply abbreviated as PA66-a] 40 parts by weight, viscosity number 130 ml / g, terminal amino group concentration 4.2 × 10 ⁵ mol / g, terminal carboxyl group 10 parts by weight of polyamide 6,6 [hereinafter simply abbreviated as PA66-b] having a concentration of 9.1 × 10 ⁵ mol / g was dry-blended with a tumbler.
At this time, the barrel temperature is set to water cooling for the first cylinder unit, 250 ° C. for the second and third cylinder units, 320 ° C. for the fourth to seventh cylinder units, and 280 ° C. for the eighth to twelfth cylinder units. Was set to 320 ° C.
These raw materials were adjusted to the composition ratios shown in Table 1 and the feed rate of each feeder was adjusted so that the total discharge rate was 909 kg / h, and melt-kneaded with an extruder to obtain pellets.
In addition, the screw rotation speed at this time was 500 rpm.

(Polyphenylene ether molecular weight measurement)
About 10 g of the obtained pellet was sliced with a microtome to a thickness of about 20 μm, and Soxhlet extracted with 50 ml of chloroform. The obtained chloroform solution (components soluble in chloroform: mainly polyphenylene ether and block copolymer) was measured with an ultraviolet spectroscopic detector using GPC, and converted into standard polystyrene for calculation. At this time, the measurement ultraviolet wavelength was set to 283 nm so as not to detect the block copolymer eluting at the same time.
When the obtained molecular weight data was analyzed, the weight ratio of the molecular weight of 200,000 or more was 1.45%, and the weight ratio of the molecular weight of 5,000 or less was 4.78%. The ratio of the ratio of the component having a molecular weight of 200,000 or more to the ratio of the component having a molecular weight of 5,000 or less was 0.30.

(Polyamide area ratio measurement)
Next, in order to determine the polyamide area ratio of the obtained pellets, the pellets were immersed in a 10% by weight aqueous solution of phosphoric-tungstic acid whose temperature was adjusted to 40 ° C. for 8 hours, and the polyamide portion was selectively dyed. And washed with water, dried, and the surface of the obtained dyed pellet was subjected to an acceleration voltage of 5 kV using a field emission scanning electron microscope FE-SEM [device name: S-4700 type / manufactured by Hitachi, Ltd.] Then, a backscattered electron image was taken at a magnification of 2500 times at an angle perpendicular to the surface. The ratio of the area reflected in white with respect to the total area of the obtained reflection electron image photograph was calculated by using an image analysis apparatus (device name: Image-Pro PLUS ver. 4.0 / manufactured by Media Cybernetics, USA), and polyamide. The area ratio is shown in Table 1. (At this time, the threshold value for binarization when calculating the area ratio of white and black was obtained by obtaining the peak value of white and black from the tone histogram and setting it as the intermediate value.)

(Molded state of molded body)
Using an IS80EPN injection molding machine set at a cylinder set temperature of 280 ° C. and a mold temperature of 80 ° C., it was formed into a flat plate-shaped piece having a width of 50 mm, a length of 90 mm, and a thickness of 2.5 mm. At this time, the injection speed (average speed of the molten resin passing through the critical cross-sectional area described in ISO294-1) is set to be 200 mm / s, and the injection pressure is necessary to fill the test piece. Molding was performed at the minimum pressure (minimum pressure at which sink marks and unfilled parts did not occur). The injection time was 20 seconds and the cooling time was 25 seconds.
When the surface state of the obtained molded piece was observed, it was almost matte except for the gate portion of the molded piece. In the present invention, the matte state was evaluated in the following four stages. In order to obtain a coating film having a uniform thickness that is easy to paste, it is preferable that the number of matte portions is larger.
I: The entire surface of the molded piece is glossy, and there is almost no matte part.
II: There is a frosted portion only at the flow end portion of the molded piece.
III: Almost matte state except near the gate of the molded piece.
IV: Almost the entire surface of the molded piece is frosted.

(Coating adhesion evaluation)
In order to measure the adhesion of the coating film, an automatic spray coating apparatus was used to adjust the coating film thickness to 20 μm, and coating on a flat molded piece was performed. The paint used was Z-NY manufactured by Origin. After spray coating, baking was performed at a temperature of 80 ° C. for 30 minutes.
After painting, leave it in an environment with a temperature of 23 ° C and a humidity of 50%, and after 24 hours, scratch it in a grid pattern with a cutter knife so that the glance is 2mm square in a range of 2cm x 2cm (total 100), a film peeling test was performed in which cellophane was applied and peeled off at once. Of the 100 eyes, the number of grids remaining without peeling after the peeling test was measured, and 95 eyes remained without peeling.
The results obtained are listed in Table 1.

(Paint clarity)
The appearance of the flat test piece after coating was observed. In the observation, first, the paint surface was observed in detail, and it was confirmed whether the paint surface had small irregularities. Next, evaluation was performed by reflecting the fluorescent lamp located about 1.5 m above the painted surface. The evaluation criteria are as follows.
Class A: The outline of the fluorescent lamp reflected on the painted surface is clearly visible.
Class B: Although the outline of the fluorescent lamp reflected on the painted surface is unclear, it can be discriminated.
Class C: The extent of the fluorescent lamp reflected on the painted surface is unclear and the presence can be confirmed.
Class D: There are small irregularities on the painted surface.
In order to measure the melt viscosity of the resin forming the dispersed phase, all the extrusion was carried out in the same manner except that only the three feeders except the feeder 4 were operated using the above-mentioned extruder, and pellets containing only the dispersed phase resin were obtained. Obtained. Next, in order to measure the melt viscosity of the resin forming the continuous phase, extrusion was carried out in a state where only the feeder 4 was operated to obtain pellets of only the continuous phase resin.
When each obtained pellet was measured for melt viscosity at 290 ° C. and 1000 sec ⁻¹ with a capillary rheometer, the dispersed phase melt viscosity (ηd) was about 1570 Pa · sec, and the continuous phase melt viscosity ( ηm) was about 50 Pa · sec. The viscosity ratio (ηd) / (nm) of both was about 31.

[ Reference Examples 2 to 5 ]
It implemented similarly to the reference example 1 except having changed the raw material to supply and its quantity as described in Table 1, and measured each physical property. The results are shown in Table 1.
The raw materials different from those used in Reference Example 1 are as follows.
Polyphenylene ether powder having a reduced viscosity of 0.42 dl / g [hereinafter simply abbreviated as PPE2]
MPPE produced in Production Example 1
Polyamide 6,6 having a viscosity number of 230 ml / g, a terminal amino group concentration of 2.4 × 10 ⁵ mol / g, and a terminal carboxyl group concentration of 4.8 × 10 ⁵ mol / g [hereinafter simply abbreviated as PA66-c]
PA66 / 6I produced in Production Example 2

[ Reference Examples 6 to 9 ]
It implemented like the reference example 1 except having used the raw material shown below. Each physical property value is shown in Table 2 together with the composition.
Polystyrene-polyethylenebutylene-polystyrene block copolymer having a number average molecular weight (Mn) of 105,000 (styrene content 60%) [hereinafter simply abbreviated as SEBS3]
Ketjen Black EC-600JD [hereinafter referred to as KB] obtained from Ketjen Black International
Polyamide / carbon masterbatch produced in Production Example 3 [hereinafter simply PA-MB]

[Example 1 and Comparative Examples 1-3]
Extrusion was performed in the same manner as in Reference Example 1 except that one screw-type weight feeder (hereinafter simply abbreviated as feeder 5) was arranged at the downstream second supply port, and wollastonite was supplied. The physical properties were evaluated using the obtained pellets. The composition and results are listed in Table 3. The raw materials different from those used in Reference Example 1 and the raw materials not used in Reference Example 1 are as follows.
Polyamide 6 obtained from Ube Industries, Ltd .: Trade name 1013B (hereinafter simply referred to as PA6)
The following Wollastonite [Wollastonite 1] obtained from Nyco, USA
Average particle size = 5 μm, aspect ratio = 13
[Wollastonite 2]
Average particle size = 5 μm, aspect ratio = 3
[Wollastonite 3]
Average particle diameter = 10 μm, aspect ratio = 13, 0.5 wt% aminosilane compound treated product

[ Example 2 ]
It implemented like the reference example 1 except having changed the ratio of each raw material. The obtained results are shown in Table 4 together with the composition.

  The resin molded body of the present invention is excellent in surface matting properties, coating film adhesion after coating, and coating film sharpness. In addition, when a molded product is produced using the conductive resin composition of the present invention, the obtained molded product not only has excellent matte surface properties but also excellent coating adhesion after coating and coating clarity. In addition, it is possible to obtain a molded article having a sufficiently low linear expansion coefficient, which is a particularly important characteristic in large molded articles such as automobile fenders and automobile back doors. The thermoplastic resin molded article of the present invention and the molded article obtained using the conductive resin composition of the present invention are not only automobile exterior parts, but also electric / electronic parts, OA parts, machine parts, and motorcycles / automobiles. It can be suitably used in a wide range of fields such as electrical parts and interior parts.

Claims (4)

Polyamide (A), polyphenylene ether (B), at least one aromatic vinyl polymer block mainly composed of aromatic vinyl monomer units and at least one conjugated diene polymer block mainly composed of conjugated diene monomer units A conductive resin composition comprising a block copolymer (C), a conductive carbon material (D), and wollastonite particles (E),
Here, the amount of each component is 50 to 70% by weight of the polyamide (A), polyphenylene ether (B) and the total weight of the partially hydrogenated block copolymer (C). B) is in the range of 25 to 45% by weight, the partially hydrogenated block copolymer (C) is in the range of 5 to 25% by weight, and the carbon material (D) is 0.5 to 2.5% by weight ,
The polyamide (A) comprises two or more kinds of polyamide components having different viscosities, and the viscosity number of the polyamide mixture is 90 to 130 ml / g,
The wollastonite particles (E) have an average particle diameter of 2 to 9 μm, and include particles having an aspect ratio of 5 or more and 13 or less , and particles having an aspect ratio of 3 or more and less than 5, and the aspect ratio The conductive resin composition, wherein the amount of the particles of 5 or more and 13 or less is 50% by weight or more based on the total weight of the wollastonite particles (E).   A master batch in which the conductive carbon material (D) is dispersed in the polyamide (A) is converted into a polyphenylene ether (B), a block copolymer (C), wollastonite particles (E), and optionally an additional amount of polyamide. Produced by melt-kneading with at least one selected from the group consisting of (A) and an additional amount of conductive carbon material (D), wherein the conductive carbon material (D) comprises conductive carbon black, carbon fibrils, and The conductive resin composition according to claim 1, wherein the conductive resin composition is at least one selected from the group consisting of carbon nanotubes. The polyphenylene ether (B) includes a relatively high molecular weight polyphenylene ether molecule having a molecular weight of 200,000 or more and a relatively low molecular weight polyphenylene ether molecule having a molecular weight of 5,000 or less. The weight ratio with respect to the low molecular weight polyphenylene ether molecule is 0.35 or less, and the amount of the relatively low molecular weight polyphenylene ether molecule and the relatively high molecular weight polyphenylene ether molecule with respect to the weight of the polyphenylene ether (B) is respectively The conductive resin composition according to claim 1, wherein the content is 5% by weight or less and 2% by weight or less. The wollastonite particles (E) are added in the form of a wollastonite-containing masterbatch obtained by dispersing in advance at least a part of the polyamide (A) and / or at least a part of the partially hydrogenated block copolymer. The conductive tree according to claim 1, wherein
A method for producing a fat composition.