KR20090037916A - Conductive resin composition and molded article obtained by molding the same - Google Patents

Abstract

Disclosed are a conductive resin composition with reduced odor, and a molded article obtained by using such a resin composition. Specifically disclosed is a conductive resin composition obtained by blending 50-200 parts by weight of a stainless steel microfiber (D) and 0.1-5.0 parts by weight of a synthetic zeolite (E) represented by the formula (1) below per 100 parts by weight of a resin component (C) containing 50-92% by weight of a polyphenylene ether (A) and 50-8% by weight of a styrene resin (B). M2/nO Al2O3 xSiO2 yH2O (1) (In the formula, M represents an ion-exchangeable monovalent or divalent metal; n represents the valence of the metal; x represents a silica coefficient (SiO2/Al2O3 molar ratio), namely a number of 10-500; and y represents the number of crystal water, namely a number of 0-7.)

Description

Conductive resin composition and molded article formed by molding it {CONDUCTIVE RESIN COMPOSITION AND MOLDED ARTICLE OBTAINED BY MOLDING THE SAME}

TECHNICAL FIELD The present invention relates to a novel conductive resin composition, and more particularly, to melt kneading of a polyphenylene ether resin composition (hereinafter sometimes abbreviated as modified polyphenylene ether resin) or a molded article containing a styrene resin. The present invention relates to a conductive resin composition which reduces odor generated at the time of high temperature heating and suppresses adhesion of dust and dust, and molded articles such as a storage container and a tray for conveying electrical and electronic components formed by molding the resin composition.

In recent years, small size, light weight, high integration, and high precision of electric, electronic, and OA devices have progressed, and along with this, there is an increasing demand for minimizing the adhesion of dust and dust to electric and electronic components. Originally, when dust or dust adheres to electrical and electronic parts, problems such as poor contact or reading errors are inherently reluctant to adhere to dust and dust. Particularly, the recent miniaturization, high integration, and high precision of electrical and electronic parts The demand is becoming more stringent. For example, solid-state imaging devices such as CCD image sensors and CMOS image sensors used in wafers, IC chips, digital cameras and video cameras used in semiconductors, and internal parts of hard disks used in computers are the best examples. The manufacture and assembly of these electrical and electronic components are usually carried out in a so-called clean room where there is very little dust or dust, and no adhesion of dust or dust occurs here. However, at the time of conveyance of an electrical and electronic component, since it is exposed to external air, adhesion of dust and dust becomes a problem. In order to avoid this problem, the use of the resin material which gave electroconductivity is calculated | required for components for conveyance and storage of an electric / electronic component (IC, CCD tray, case, housing, etc.).

On the other hand, the process of manufacture of resin composition, injection molding, etc. is normally performed at high temperature, for example, it is 200-280 degreeC with styrene resin, 260 degreeC-360 degreeC with polyphenylene ether, and modified polyphenylene ether. In resin, it will be in a molten state at 240-350 degreeC high temperature in many cases.

Moreover, the molded article obtained by shape | molding such a resin composition is often exposed to high temperature in the use process. For example, in the case of a tray in which the molded article is used in an IC or CCD manufacturing process and a transport process, some moisture contained in the IC or CCD or volatile impurities such as alkali ions, Br ions, and Cl ions are degassed and removed. In order to carry out (baking), an IC or CCD is placed in the tray and used by heating in a baking chamber set at a temperature of 130 ° C or higher. If moisture or gaseous components remain in the IC or CCD, defects that are fatal to the accuracy of the IC or CCD are brought about. Therefore, it is necessary to heat sufficiently in this baking step. Recently, in order to improve the reliability of IC and CCD, the baking temperature tends to rise to 150 ° C or higher.

In addition, at the time of high temperature heating, such as melt kneading of a resin composition, shaping | molding process, baking of a molded article, (1) odor derived from a small amount of manufacturing raw materials which remain in resin, (2) odor by thermal decomposition of resin, (3) additive Odor due to thermal decomposition or vaporization of In addition, there is a problem that such odor harms the production chamber, the molding processing chamber and the surrounding environment of the resin composition. In addition, this odor is brought into a clean room with limited ventilation, together with molded products such as ICs and CCD trays, and there is also a problem that remarkable discomfort is caused to the assembling worker of the electrical and electronic parts. Therefore, the low odor conductive resin composition is calculated | required by the tray for conveyance of an electric and electronic component.

In order to give electroconductivity to modified polyphenylene ether resin, mix | blending electroconductive carbon black and metal fiber is widely performed. Although the patent document 1 or 2 can be illustrated as modified polyphenylene ether resin which mix | blended electroconductive carbon black, there exist the following faults. (1) Desorption of carbon black (so-called `` carbon black deterioration '') occurs due to abrasion during contact and friction of molded products, and the desorbed carbon black is used in ICs, CCD chips, wafers, and computers. It is attached to the internal parts of the hard disk and causes a malfunction. (2) Odor is generated when the resin composition or the molded article is heated to a high temperature. (3) Deterioration of the appearance of the molded article is caused by a decrease in mechanical strength, a decrease in moldability, and exposure of carbon black. (4) Since only a black resin composition can be obtained, it is impossible to identify molded articles by coloring them in various colors.

Moreover, when metal fiber longer than 1 mm is mix | blended with resin, the dispersion defect by entanglement of a metal fiber easily arises, and it becomes a cause of a deviation of electroconductivity and a blockage of a gate.

Resin composition which mix | blended 1 mm or less metal fiber as a conductive resin composition which solved the various problem by said carbon black and the dispersion defect of metal fiber is disclosed in patent document 3, but is used by the patent document 3 The length of the metal fiber is also long, so that the blockage occurs, and the problem of odor generated when the resin composition or the molded article is heated to a high temperature is not solved.

For the purpose of solving the odor problem, a modified polyphenylene ether resin is blended with carbon black and a synthetic zeolite having a water adsorption capacity of 20% by weight or more under conditions of a pore diameter of 0.8 nm or more and a temperature of 25 ° C / relative humidity of 10% / atmospheric pressure. The resin composition (patent document 4) is disclosed. However, about the synthetic zeolite of patent document 4, only the water adsorption capacity is attracting attention, and it is not paying attention about the silica coefficient and crystal quantity of a zeolite, and it does not specifically describe. In addition, only examples using hydrophilic zeolites having a low silica coefficient are described.

In addition, Patent Document 5 is an additive for resin comprising, as a main component, an inorganic powder capable of deodorizing and removing odors generated during kneading and molding of a resin composition, and as an inorganic powder, silica, metal oxide, The use of aluminosilicates with alumina is disclosed. However, in the resin composition in which the additive for resins specifically described in patent document 5 was mix | blended, there is no description regarding the external appearance and mechanical strength of a molded article, and the inorganic powder used in the Example was low in silica coefficient.

Patent Document 1: Japanese Patent Application Laid-open No. Hei 2-175754

Patent Document 2: Japanese Unexamined Patent Publication No. 2004-263016

Patent Document 3: Japanese Patent Application Laid-Open No. 2-178336

Patent Document 4: Japanese Patent Application Laid-Open No. 07-138466

Patent Document 5: Japanese Patent Application Laid-Open No. 11-293032

Disclosure of the Invention

Problems to be Solved by the Invention

As a result of the present inventor's further examination of the said patent document 4, when synthetic zeolite whose water adsorption capacity is 20 weight% or more described in patent document 4 is used, silver generate | occur | produces on the surface of a molded article, and appearance is inferior. Only a molded article was obtained, and the problem of carbon black peeling was not solved.

Moreover, when this inventor examined further about the resin composition of patent document 5, it turned out that the problem of the fall of an inorganic powder is not solved.

The problem to be solved by the present invention is that it can be colored in a color other than black without compromising the original properties of the modified polyphenylene ether resin, the appearance of the molded article is excellent, during melt kneading and molding processing of the resin, etc. It is providing the electrically-conductive resin composition by which generation | occurrence | production of the odor at the time of high temperature heating of the resin molded article at the time of high temperature heating, and the molded article using this resin composition were reduced.

Means to solve the problem

The present inventors, as a result of intensive studies to solve the above problems, by combined use of a hydrophobic having a particular shape metal fibers with high SiO ₂ / Al ₂ O ₃ molar ratio of the high silica-alumina-silicate synthetic zeolite, the above-mentioned problems I found something that could be solved.

That is, 50-200 weight of stainless steel microfibers (D) with respect to 100 weight part of resin components (C) containing 50-92 weight% of polyphenylene ether (A) and 50-8 weight% of styrene-type resin (B). The resin composition formed by mixing 0.1 to 5.0 parts by weight of the synthetic zeolite (E) represented by the following formula and the following formula (1) does not impair the original properties of the modified polyphenylene ether resin, but does not impair the melt kneading and molding of the resin Generation of odor at the time of high temperature heating of the resin and the high temperature heating of the resin molded article can be remarkably reduced, coloration other than black is also possible, and it is found that the appearance of the molded article is also very excellent in the conductive resin composition. It is reached.

_{M 2 / n O · Al 2} O 3 · xSiO 2 · yH 2 O (1)

(Wherein M represents an ion-exchangeable monovalent or divalent metal, n represents the valence of the metal, and x represents a number from 10 to 500 in terms of silica coefficient (molar ratio of SiO ₂ / Al ₂ O ₃ ). Y represents the number of 0-7 in the number of crystallized water)

Effects of the Invention

Since the low odor conductive resin composition of the present invention can maintain the original properties of the modified polyphenylene ether resin and can be colored, and has a small amount of adhesion of dust and dust, and has stable conductivity, the storage container for electric and electronic components is particularly It is suitable as a material for conveyance trays, etc. Moreover, since the resin composition and the molded article using the resin composition generate | occur | produce little odor at the time of high temperature heating, and can maintain a comfortable working environment in the clean room with limited ventilation, electrical and electronic components, such as IC and CCD, are especially It is very suitable for manufacture of molded articles, such as a tray for conveyance.

Best Mode for Carrying Out the Invention

EMBODIMENT OF THE INVENTION Below, the content of this invention is demonstrated in detail. In addition, in this specification, "-" is used by the meaning which includes the numerical value described before and after that as a lower limit and an upper limit. In this specification, unless otherwise indicated, "group", such as an alkyl group, may have a substituent, and does not need to have it.

Polyphenylene ether (A) in this invention is a polymer which has an aromatic polyether structure, Preferably it is following formula (2)

[Formula 1]

(In formula, R <_1> represents a C1-C3 lower alkyl group, R <_2> and R <_3> represent a hydrogen atom or a C1-C3 lower alkyl group, respectively.)

As a polymer which has a structural unit represented by the main chain, a homopolymer or a copolymer may be sufficient.

As R ₁ , a methyl group and an ethyl group are preferable.

When R <_2> and R <_3> is a C1-C3 lower alkyl group, a methyl group and an ethyl group are preferable.

Examples of the polyphenylene ether (A) include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly ( 2,6-dipropyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2-methyl-6-propyl-1,4-phenyl Homopolymers such as ethylene) ether, and copolymers such as various 2,6-dialkylphenol / 2,3,6-trialkylphenol copolymers, and poly (2,6-dimethyl-1, 4-phenylene) ether and 2,6-dimethylphenol / 2,3,6-trimethylphenol copolymer are preferable. Moreover, polyphenylene ether containing the molecular structural part which improves characteristics, such as molecular weight, melt viscosity, impact resistance, is also preferable.

It is preferable that the intrinsic viscosity of 30 degreeC measured in chloroform is 0.2-0.8 dl / g, and, as for the polyphenylene ether (A) used by this invention, it is more preferable that it is 0.3-0.6 dl / g. By setting the intrinsic viscosity to 0.2 dl / g or more, the mechanical strength of the resin composition tends to be improved, and by setting it to 0.8 dl / g or less, the fluidity improves and the molding process tends to be easy.

Examples of the styrene resin (B) used in the present invention include polymers of styrene monomers, copolymers of styrene monomers and other copolymerizable monomers, styrene graft copolymers, and the like.

As a styrene-type monomer, styrene, (alpha) -methylstyrene, p-methylstyrene, etc. are mentioned, for example, Preferably styrene is mentioned. As a monomer which can be copolymerized with a styrene-type monomer, For example, vinyl cyanide monomers, such as an acrylonitrile and methacrylonitrile, methyl acrylate, ethyl acrylate, propyl acrylate, methyl methacrylate, ethyl methacrylate, etc. A meth) acrylic-acid alkylester monomer, maleimide, N-phenylmaleimide, etc. are mentioned, Preferably, a cyanide vinyl monomer and a (meth) acrylic-acid alkylester monomer are mentioned.

As a copolymer of a styrene-type monomer and another copolymerizable monomer, a styrene acrylonitrile resin (AS resin) etc. are mentioned, for example, As a styrene-type graft copolymer, it is an impact-resistant polystyrene (HIPS resin, for example). ), Acrylonitrile / butadiene / styrene resin (ABS resin), AES resin in which butadiene of said ABS resin was substituted with ethylene-propyne type rubber, acrylonitrile / acrylate / styrene resin (AAS resin), etc. are mentioned. . As a manufacturing method of a styrene-type copolymer, well-known methods, such as emulsion polymerization method, solution polymerization method, suspension polymerization method, or block polymerization method, are mentioned.

As styrene resin (B), polystyrene and impact resistant polystyrene are preferable at the point of compatibility with polyphenylene ether. In particular, when impact resistance is required, impact polystyrene is more preferable.

The resin component (C) in this invention contains 50-92 weight% of polyphenylene ether (A) and 50-8 weight% of styrene-type resin (B). Preferably it contains 60 to 90 weight% of polyphenylene ether (A) and 40 to 10 weight% of styrene resin (B), More preferably, 70 to 90 weight% of polyphenylene ether (A) and styrene It contains 30-10 weight% of system resin (B). If the polyphenylene ether (A) is less than 50% by weight, the load bending temperature and the mechanical strength tend to be lowered. If the polyphenylene ether (A) is higher than 92% by weight, the fluidity is lowered and the molding process tends to be complicated.

In order to improve impact strength, it is preferable to mix | blend a styrene-type elastomer with the resin component (C) in this invention further. The styrene-based elastomer preferably blended in the present invention is a block copolymer in which the hard segment is composed of a styrene polymer and the soft segment is composed of at least one polymer selected from the group consisting of polybutadiene, polyisoprene and their hydrogenated materials, specifically SBS (styrene / butadiene / styrene block copolymer), SIS (styrene / isoprene / styrene block copolymer), SEBS (styrene / ethylene / butylene / styrene block copolymer: SBS hydrogenated material), SEPS (styrene / Ethylene / propylene / styrene block copolymers: hydrogenated SIS) and the like, and particularly preferably SEBS.

The composition ratio of the hard segment and the soft segment of the styrene-based elastomer can be appropriately selected within the range of 10 to 90 to 90 to 10 (molar ratio), preferably 10 to 90 to 50 to 50, and the hard segment block and the soft segment The combined form of the segment blocks may be a diblock type or a treeblock type.

The number average molecular weight of the styrenic elastomer is preferably 20,000 to 180,000, more preferably 30,000 to 160,000, still more preferably 35,000 to 140,000. By setting the number average molecular weight to 20,000 or more, the impact resistance and dimensional stability of the finally obtained resin composition can be excellent, and the appearance of the molded article obtained from the resin composition can also be improved. Moreover, since the fluidity | liquidity of the resin composition finally obtained improves and molding process becomes easy by setting a number average molecular weight to 180,000 or less, it is preferable.

The compounding quantity of a styrene-type elastomer is mix | blended so that it may become 1 to 25 weight% in a resin component (C), Preferably it is 3 to 20 weight%, More preferably, it is 5 to 15 weight%. By making the compounding quantity of a styrene-type elastomer into 1 weight% or more, there exists a tendency for impact strength to improve more. Moreover, when the compounding quantity of a styrene-type elastomer is 25 weight% or less, there exists a tendency for the rigidity of a resin composition and the load deflection temperature to improve, and it is preferable.

Moreover, the resin component (C) used by this invention may contain the other resin component in the range which does not deviate from the meaning of this invention. The compounding quantity in this case is 50 weight% or less of a resin component (C) normally.

In this invention, stainless steel microfiber (D) is mix | blended for the purpose of providing electroconductivity with respect to a resin composition. Although the kind of stainless steel used as a raw material of the stainless steel microfiber (D) used by this invention is not restrict | limited, Especially SUS304, SUS316, SUS403, and mixtures thereof in JIS specification are preferable.

The average fiber length of a stainless steel microfiber (D) becomes like this. Preferably it is 50-500 micrometers, More preferably, it is 100-300 micrometers. When the average fiber length is 50 µm or more, the conductive effect tends to be improved, and when the average fiber length is 500 µm or less, dispersion failure due to entanglement between fibers occurs, and variations in conductivity and gate clogging during molding are less likely to occur. The strength tends to be improved.

The average fiber diameter of a stainless steel microfiber (D) becomes like this. Preferably it is 1-50 micrometers, More preferably, it is 10-30 micrometers, Especially preferably, it is 10-20 micrometers. When the average fiber diameter is 1 μm or more, the fibers are not easily broken, and when the average fiber diameter is 50 μm or less, the conductive effect is improved and the appearance tends to be improved. In addition, the average fiber length and average fiber diameter of the stainless steel microfiber in this invention disperse | distribute the stainless steel microfiber of a raw material on a slide glass, observe by a microscope, and take a picture, The obtained photograph is image analysis software It is a number average value of the value obtained by measuring fiber length and fiber diameter about 2000 stainless steel microfibers using (Plantron Corporation "Image-Pro Plus").

It is preferable that the specific gravity of stainless steel microfiber (D) is 7.7-8.0.

The stainless steel microfiber (D) used by this invention can also be processed with surface treating agents, such as a coupling agent used as a surface treating agent of glass fiber.

Since the stainless steel microfiber (D) of this invention has less bleed out on the surface of a molded article compared with the conductive carbon black etc. which are conventionally used for imparting electroconductivity, surface appearance is favorable and there is little fallout. Moreover, since the volume ratio with respect to a compounding quantity is small, the dispersibility in a resin composition is also favorable, and an electroconductivity deviation, a molded product color nonuniformity generate | occur | produce, or a mechanical strength falls by poor dispersion. In the present invention, in particular, the above-described performance can be more effectively exhibited by using a stainless steel microfiber (D) having a short average fiber length of about 100 to 300 µm.

The compounding quantity of a stainless steel microfiber (D) is 50-200 weight part with respect to 100 weight part of resin components (C), Preferably it is 60-150 weight part, More preferably, it is 60-120 weight part. When the compounding quantity is 50 parts by weight or more, the surface resistance value is drastically lowered, and the conductive effect tends to be improved. Moreover, specific gravity will fall by setting it as 200 weight part or less, and there exists a tendency for mechanical strength to improve.

In the present invention, the synthetic zeolite (E) is mainly intended to reduce the odor derived from the residual production raw material, the odor due to thermal decomposition of the resin, the odor due to thermal decomposition or vaporization of the additive, and the like, which are generated from the resin composition during high temperature heating. Compound. Synthetic zeolite (E) used by this invention is an aluminosilicate generally comprised by the three-dimensional skeleton structure, and is represented by following formula (1).

_{M 2 / n O · Al 2} O 3 · xSiO 2 · yH 2 O (1)

(Wherein M represents an ion-exchangeable monovalent or divalent metal, n represents the valence of the metal, and x represents a number from 10 to 500 in terms of silica coefficient (molar ratio of SiO ₂ / Al ₂ O ₃ ). Y represents the number of 0-7 in the number of crystallized water)

Zeolites include natural zeolites and synthetic zeolites, and synthetic zeolites have a low silica coefficient (less than 10) of hydrophilic zeolites (for example, A-type zeolites, X-type zeolites, Y-type zeolites, etc.), and high silica coefficients ( 10 or more) hydrophobic zeolites (e.g., MFI zeolites), and the synthetic zeolites (E) used in the present invention are hydrophobic zeolites, and are readily available on the market, Synthetic zeolites are preferred. The hydrophobic MFI-type synthetic zeolite has a three-dimensional network structure in which the inlet of the pores is formed of a 10-membered oxygen ring, and consists of linear pores and zigzag pores intersecting them, for example, effective pores. An oval having a diameter of 5 to 6 mm 3 is preferably an pore volume of 0.15 to 0.25 ml / g and a specific surface area of 300 to 550 m 2 / g. An oval having an effective pore diameter of 5 to 6 mm 3 is a pore volume of 0.15 to 0.25 ml / g. It is more preferable that it is 300-450 m <2> / g in surface area.

The synthetic zeolite (E) used by this invention needs to be represented by said formula (1), and silica coefficient x becomes like this. More preferably, it is 20-60, More preferably, it is 30-60. Moreover, it is preferable that M of Formula (1) is sodium, potassium, or calcium, and it is more preferable that it is sodium. It is preferable that the value of y of Formula (1) is low.

In addition, the synthetic zeolite (E) used in the present invention preferably has a water adsorption capacity under a condition of a temperature of 25 ° C./relative humidity 10% / atm, preferably less than 20% by weight, more preferably less than 15% by weight, even more preferably. Is a synthetic zeolite of less than 10% by weight. In particular, the synthetic zeolite represented by the above formula (1) and having a silica coefficient x of 20 to 60 and a water adsorption capacity of less than 10% by weight under conditions of a temperature of 25 ° C / relative humidity of 10% / atmospheric pressure has high heat resistance and hydrophobicity. The molded article obtained from the low malodorous resin composition in which the synthetic zeolite is blended has no characteristic of generating silver and is also excellent in appearance.

Preferably the average primary particle diameter of the synthetic zeolite (E) which concerns on this invention is 0.1-20 micrometers, More preferably, it is 0.2-10 micrometers, More preferably, it is 0.5-5 micrometers. By setting the average primary particle diameter of the synthetic zeolite (E) to 0.1 µm or more, the melt viscosity of the resin composition tends to be low, and by setting it to 20 µm or less, the surface roughness of the molded article becomes less visible and the appearance is improved. It tends to be preferable.

The compounding quantity of a synthetic zeolite (E) is 0.1-5.0 weight part with respect to 100 weight part of resin components (C), Preferably it is 0.2-3.0 weight part. If the blending amount is less than 0.1 part by weight, the effect of reducing malodor is small, and even if blended in excess of 5.0 parts by weight, the effect of further reducing the malodor cannot be expected, and there is a problem that the mechanical strength is also lowered.

In the low odor conductive resin composition of the present invention, in addition to the above components, colorants such as pigments and dyes, aliphatic carboxylic acids, aliphatic carboxylic acid esters, release agents such as polyolefin waxes and silicone oils, and hindered phenol compounds Stabilizers such as phosphorus compounds and zinc oxide, flame retardants such as phosphate esters and condensed phosphate esters, ultraviolet absorbers such as hindered amines, benzotriazoles, benzophenones, and epoxys, antioxidants, lubricants, plasticizers, antistatic agents, Additives such as a sliding improver, a compatibilizer, a difluoroethylene polymer, a tetrafluoroethylene polymer, a tetrafluoroethylene-hexafluoropropylene copolymer, an air of tetrafluoroethylene and an ethylene monomer containing no fluorine Fluorinated resins, glass fibers, glass flakes, which have a drip-preventing effect during resin combustion, Carbon fibers, stainless steel micro-reinforcing filler such as a metal fiber other than the fiber or potassium titanate, aluminum borate, whiskers, mica, talc, such as calcium silicate, may be added inorganic fillers such as clay. The compounding method of these additives can be suitably performed by the conventionally well-known method which utilizes these characteristics.

In this invention, a coloring agent (F) can be added. In the conventional electrically conductive resin composition, since carbon black was employ | adopted in order to provide electroconductivity, there were many cases which can obtain only a black resin composition. However, in this invention, since electroconductivity can be provided without using conductive carbon black, it can color freely.

As a coloring agent (F) in this invention, dye, an inorganic pigment, and an organic pigment generally used for a thermoplastic resin are mentioned.

Examples of the dyes include azo dyes, anthraquinone dyes, phthalocyanine dyes, indigo dyes, diphenylmethane dyes, acridine dyes, cyanine dyes, nitro dyes and nigrosine. Examples of the inorganic pigments include oxide pigments such as titanium oxide, bengal and cobalt blue, hydroxide pigments such as alumina white, sulfide pigments such as zinc emulsion and cadmium yellow, silicate pigments such as white carbon and talc, and carbon black. As an organic pigment, a nitro pigment, an azo pigment, a phthalocyanine pigment, a condensation polycyclic pigment, etc. are mentioned. Among these, an inorganic pigment is preferable at the point which is hard to bleed out on the molded article surface. Moreover, you may use also the coloring agent master-arranged with thermoplastic resins, such as a polyphenylene ether resin, a polystyrene resin, a polycarbonate resin, and an acrylic resin, for the purpose of the handleability improvement at the time of extrusion.

0.01-20 weight part is preferable with respect to 100 weight part of resin components (C), and, as for the compounding quantity of a coloring agent (F), 0.1-15 weight part is more preferable. Moreover, inorganic pigments, such as titanium oxide, may be used for other than coloring purpose (for example, light-shielding property), and the compounding quantity in that case is 5-5 normally with respect to 100 weight part of resin components (C). 20 parts by weight, preferably 5 to 15 parts by weight. You may use together these 2 or more types of coloring agents.

As a stabilizer in this invention, a hindered phenol type compound, a phosphorus type compound, zinc oxide, etc. are mentioned, for example.

Specific examples of the hindered phenol compound include n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate and 1,6-hexanediol-bis [3- (3 , 5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,6-di-tert-butyl-4-methylphenol, 3,9-bis [1,1-dimethyl-2- {β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyl Oxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) prop Cionate], 3,5-di-tert-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert -Butyl-4-hydroxybenzyl) benzene, 2,2-thio-diethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], tris (3,5 -Di-tert-butyl-4-hydroxybenzyl) -isocyanurate, N, N'-hex Methylene-bis-, and the like (3, 5-di -tert- butyl-4-hydroxy-dihydro-cinnamic amide). Among them, n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,6-hexane diol-bis [3- (3,5-tert-butyl -4-hydroxyphenyl) propionate], 2,6-di-tert-butyl-4-methylphenol, 3,9-bis [1,1-dimethyl-2- {β- (3-tert-butyl 4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane is preferred.

As a phosphorus compound, it is preferable to use a phosphonite compound and a phosphite compound, for example.

Examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylenediphosphonite and tetrakis (2,5-di-tert-butylphenyl ) -4,4'-biphenylenediphosphonite, tetrakis (2,3,4-trimethylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,3-dimethyl-5- Ethylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butyl-5-ethylphenyl) -4,4'-biphenylenediphosphonite, tetrakis ( 2,3,4-tributylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,4,6-tri-tert-butylphenyl) -4,4'-biphenylenediphospho Nitrate etc. are mentioned, Especially, tetrakis (2, 4-di-tert- butylphenyl) -4, 4'-biphenylenediphosphonite is preferable.

Examples of the phosphite compound include tris (2,4-di-tert-butylphenyl) phosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite and bis (2,6- Di-tert-butyl-4-methylphenyl) pentaerythritoldiphosphite, 2,2-methylenebis (4,6-di-tert-butylphenyl) octylphosphite, 4,4'-butylidenebis (3- Methyl-6-tert-butylphenylditridecyl) phosphite, 1,1,3-tris (2-methyl-4-ditridecylphosphite-5-tert-butyl-phenyl) butane, tris (nonylphenyl) Phosphite, 4,4'-isopropylidenebis (phenyldialkyl phosphite), and the like; tris (2,4-di-tert-butylphenyl) phosphite, 2,2-methylenebis (4, 6-di-tert-butylphenyl) octylphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite and the like are preferable.

As zinc oxide, it is preferable that average particle diameters are 0.02-1 micrometer, for example, and it is more preferable that average particle diameters are 0.08-0.8 micrometer.

Among these stabilizers, zinc oxide is preferred in that mold deposits are hardly generated and are not easily discolored.

The compounding quantity of a stabilizer becomes like this. Preferably it is 0.01-5 weight part, More preferably, it is 0.05-3 weight part with respect to 100 weight part of resin components (C). By setting the blending amount to 0.01 parts by weight or more, the effect as a stabilizer can be sufficiently exhibited, and by setting it as 5 parts by weight or less, the decrease in mechanical strength and the generation of mold deposits during molding can be suppressed. You may use these stabilizers together 2 or more types.

As a mold release agent in this invention, aliphatic carboxylic acid, aliphatic carboxylic acid ester, polyolefin wax, silicone oil, etc. are mentioned, for example.

As aliphatic carboxylic acid, saturated or unsaturated aliphatic monocarboxylic acid, dicarboxylic acid, or tricarboxylic acid is mentioned. Aliphatic carboxylic acid here also contains alicyclic carboxylic acid. Among these, preferable aliphatic carboxylic acid is C6-C36 mono or dicarboxylic acid, and C6-C36 aliphatic saturated monocarboxylic acid is more preferable. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, valeric acid, caproic acid, capric acid, lauric acid, arachinic acid, behenic acid, lignoseric acid, sertinic acid, melic acid, tetra Triaconic acid, montanic acid, glutaric acid, adipic acid, azelaic acid, etc. are mentioned.

As an aliphatic carboxylic acid component which comprises aliphatic carboxylic acid ester, the thing similar to the said aliphatic carboxylic acid can be used. On the other hand, as an alcohol component which comprises aliphatic carboxylic acid ester, saturated or unsaturated monohydric alcohol, saturated or unsaturated polyhydric alcohol, etc. are mentioned. These alcohols may have substituents, such as a fluorine atom and an aryl group. Among these alcohols, monohydric or polyhydric saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols or polyhydric alcohols having 30 or less carbon atoms are preferable. Aliphatic alcohols here also include alicyclic alcohols.

Specific examples of these alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol and neophene. Tylene glycol, ditrimethylol propane, dipentaerythritol, etc. are mentioned. These aliphatic carboxylic acid esters may contain aliphatic carboxylic acid and / or alcohol as impurities, or may be a mixture of a plurality of compounds.

Specific examples of the aliphatic carboxylic acid esters include beeswax (a mixture mainly composed of myristyl palmitate), stearyl stearate, behenyl behenyl, octyl dodecyl benzate, glycerin monopalmitate, glycerin monostearate, and glycerin distea And latex, glycerin tristearate, pentaerythritol monopalmitate, pentaerythritol monostearate, pentaerythritol distearate, pentaerythritol tristearate, and pentaerythritol tetrastearate.

Examples of the polyolefin waxes include homopolymers and copolymers of olefins. As a homopolymer of an olefin, polyethylene wax, a polypropylene wax, etc., these partial oxides, a mixture thereof, etc. are mentioned, for example. Examples of the copolymer of olefins include ethylene, propylene, 1-butene, 1-hexene, 1-decene, 2-methylbutene-1,3-methylbutene-1,3-methylpentene-1,4-methylpentene-1 and the like. Copolymers such as α-olefins, monomers copolymerizable with these olefins, for example, unsaturated carboxylic acids or acid anhydrides thereof [maleic anhydride, (meth) acrylic acid, etc.], (meth) acrylic acid esters [(meth) And copolymers with polymerizable monomers such as alkyl esters of 1 to 6 carbon atoms of (meth) acrylic acid such as methyl acrylate and ethyl (meth) acrylate. Moreover, these copolymers contain a random copolymer, a block copolymer, or a graft copolymer. The olefin copolymer is usually a copolymer of ethylene and at least one monomer selected from other olefins and polymerizable monomers. Of these polyolefin waxes, polyethylene wax is most preferred. Moreover, a linear or branched structure may be sufficient as polyolefin wax.

As silicone oil, the thing which consists of polydimethylsiloxane, a part or all part of the methyl group of polydimethylsiloxane, has a phenyl group, a hydrogen atom, a C2 or more alkyl group, a halogenated phenyl group, the silicone oil substituted by the fluoroester group, an epoxy group An epoxy modified silicone oil, the amino modified silicone oil which has an amino group, the alcohol modified silicone oil which has an alcoholic hydroxyl group, the polyether modified silicone oil which has a polyether structure, etc. are mentioned, You may use together two or more types.

0.01-10 weight part is preferable with respect to 100 weight part of resin components (C), as for the compounding quantity of a mold release agent, 0.1-6 weight part is more preferable, 0.1-3 weight part is more preferable. When the amount is 0.01 parts by weight or more, the releasing effect is more easily exhibited. When the amount is 10 parts by weight or less, problems such as heat resistance, mold contamination, and plasticization failure are less likely to occur.

As a method for obtaining the conductive resin composition of the present invention, for example, (1) various kinds of kneaders, for example, uniaxial and multiaxial kneaders, Banbury mixers, rolls, brabender flasks and the like, the components and A method of collectively melt kneading the additives added as necessary, (2) a method of kneading the above components and some of the additives added as necessary beforehand, and then further kneading with the other components (method using a master batch (3) The additive added as needed is dissolved in a suitable solvent such as hexane, heptane, benzene, toluene, xylene or the like and a derivative thereof, or a resin component in suspension The solution mixing method etc. which mix with C) are mentioned. Although the melt kneading method of (1) and (2) is preferable from an industrial cost point, it is not limited to this. In melt kneading, it is preferable to use a single screw or twin screw extruder.

As a method of molding a molded article molded using the conductive resin composition of the present invention, for example, a container for storing an electrical and electronic component or a tray for conveyance, an injection molding method is often used in terms of good productivity, but is particularly limited. In addition, the shaping | molding methods generally used, for example, the shaping | molding methods, such as blow molding, extrusion molding, thermoforming from a sheet-like molded article, rotation molding, can also be applied.

Examples of the molded article molded by using the conductive resin composition of the present invention include a container for transporting or storing electrical and electronic components such as an IC or CCD tray, a case, a housing, or a tray for transporting, in particular, at a high temperature such as baking. The conductive resin composition of this invention is preferable for the tray of IC or CCD used.

When the Charpy impact strength of the resin composition of this invention is measured by the method of mentioning later, it is preferable that it is 20 kJ / m <2> or more. Moreover, when the load deflection temperature of the resin composition of this invention is measured by the method of mentioning later, it is preferable that it is 155 degreeC or more.

Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to a following example, unless the summary is exceeded. Evaluation of the resin composition and the molded article in an Example and a comparative example was performed as follows.

(1) Odor A: During melt kneading of the resin composition carried out under the manufacturing conditions described below, five people take odor at a point 50 cm away from a die of a twin screw extruder (screw diameter 30 mm), and an evaluation point is given based on the following criteria. The total point of power supply was made into the evaluation point.

Odor B: The ISO test piece for the Charpy impact test obtained under the post-molding condition was put into a 300 ml orthogonal flask, and heated at 140 ° C. for 3 hours, and five people took the odor and gave evaluation points based on the following criteria. The total point of power supply was made into the evaluation point.

Evaluation Point Evaluation Criteria

1 point very fine odor

2-point fine odor

3 points easily feel bad smell

4 points strong odor

5 points very strong odor

(2) Gate occlusion: A mold having a gate having a gate diameter of 0.7 mm and a gate land of 2.0 mm in the center of a disc having a thickness of 1.0 mm and a diameter of 50 mm, using a cylinder set temperature of 290 to 330 ° C and a mold temperature of 120 ° C. Then, 500 shots were continuously injection-molded under the conditions of a molding cycle of 30 seconds, and it was investigated how many shots a gate clogging occurs. It was shown in Table 1 as "> 500" that clogging did not occur even at 500 shots.

(3) Appearance of the molded article: The appearance state of silver, flow mark, etc. of a plate molded article 50 mm × 90 mm × 3.2 mmt in width and length obtained under late molding conditions is visually observed, and in order from a molded article having excellent appearance. It evaluated in three steps of (circle), (triangle | delta), and x as follows.

(Circle): There are no appearance defects, such as silver and a flow mark.

(Triangle | delta): The external appearance defects, such as silver and a flow mark, can be seen slightly.

X: Appearance defects, such as silver and a flow mark, are outstanding.

(4) Charpy impact strength: Using the ISO test piece for Charpy impact test obtained under the post-molding conditions, it measured 5 pieces at 23 degreeC according to ISO527 standard, and showed the Charpy impact strength (hereinafter abbreviated as impact strength) with five average values. .

(5) Load deflection temperature: The load deflection temperature (hereinafter abbreviated as DTUL) was measured on condition of 1.82 MPa according to ISO75 standard using the ISO test piece for load deflection temperature test obtained under post-molding conditions.

(6) Surface resistivity: Measured at any of three points with a Lorestar or Hyrestar made by Mitsubishi Chemical Co., Ltd., using a plate-formed product having a width of 50 mm x 90 mm x 3.2 mmt obtained under late molding conditions. Was carried out. The high resistor was used for the surface resistivity to be 10 ⁴ ohms or more, and the low resta was used for the surface resistivity or less.

(7) Tape peelability: Nichiban Co., Ltd. product, brand name "Cello tape (registered trademark) CT405A were used for the surface of a molded article, using the plate-molded article which is 50 mm x 90 mm x 3.2 mmt, obtained by late molding conditions. -18 "was attached, and the peeling state of the molded article surface at the time of peeling it was visually observed, and it evaluated in three steps of (circle), (triangle | delta), and x below. As peeling is small, it can be judged that there is little peeling of stainless steel microfiber or carbon black.

(Circle): Even if a cello tape is attached, and it rubs off with force, it peels off at the surface of a molded article at all.

(Triangle | delta): Peeling generate | occur | produces on the molded article surface, when a cello tape is affixed, and it rubs off with force.

X: Peeling arises on the molded article surface only by attaching a cello tape and rubbing lightly.

[Raw materials]

The raw material shown next was prepared.

(1) Poly (2,6-dimethyl-1,4-phenylene) ether resin: Mitsubishi Engineering Plastics Co., Ltd. make, brand name "PX100F", intrinsic viscosity 0.38 dl / g (measured at 30 degreeC in chloroform) (following) I abbreviate as `` PPE '')

(2) Styrene resin: High impact polystyrene: Toyo styrol company make, brand name "H485", weight average molecular weight 200,000, MFR 3.2g / 10min (hereinafter abbreviated as "HIPS")

(3-1) Stainless steel microfiber: JFE Techno Research Co., Ltd. make, brand name "SMF-708AE", average fiber length 150 micrometers, average fiber diameter 15 micrometers, specific gravity 7.9 (hereinafter abbreviated as "SMF")

(3-2) (Comparative Example) Stainless Steel Fiber: Master pellet of stainless steel fiber, manufactured by Toyo Ink Co., Ltd., trade name "Rioconductor", stainless steel fiber having a diameter of 8 µm, and converged with polyester, Cut to pellet length 4mm, stainless steel fiber content 75% by weight (hereinafter abbreviated as `` SUS '')

(3-3) Carbon black: The product made by Ketjen Black International, brand name "Ketchen Black EC", 30 micrometers of average particle diameters (it abbreviates as "CB" hereafter).

(4-1) MFI-type synthetic high silica zeolite: Mizusawa Chemical Industry Co., Ltd. make, brand name "Mizukashibus EX-122", M in said formula (1) is sodium, n is 1 And silica coefficient x = 33, and the number of crystal water y = 0-7. In addition, the effective pore diameter was 5 to 6 kPa, and the pore volume was 0.15 to 0.25 ml / g, specific surface area 300 to 450 m 2 / g, average primary particle diameter 2.0 µm, temperature 25 ° C / relative humidity 10% / atmospheric pressure. 7% by weight of water adsorption capacity (hereinafter abbreviated as `` M zeolite '')

(4-2) (for comparative example) X-type zeolite: Nippon Chemical Industry Co., Ltd. make, brand name "Zeostar NX-110P", silica coefficient x = 2.6, effective pore diameter of 9 kPa, average primary particle diameter 3 micrometers, temperature 25 wt% of water adsorption capacity under the conditions of 25 ° C / relative humidity 10% / atmospheric pressure (hereinafter abbreviated as `` X zeolite '')

(5) Release agent: Polyethylene wax, Sanyo Kasei Kogyo Co., Ltd. brand name "acid wax 151P", density 0.93 g / ml, weight average molecular weight 2,000 (hereinafter abbreviated as "release agent")

(6) Stabilizer: Zinc oxide (Reagent 1), manufactured by Honjo Chemical Co., Ltd. (hereinafter abbreviated as "stabilizer")

(7) Coloring agent: Red inorganic pigment, the Toda Kogyo Co., Ltd. make, brand name "140ED"

[Method for Producing Resin Composition]

Cylinder setting temperature 270-320 degreeC using the composition which adjusted the said raw material to the compounding ratio shown in Table 1 using Tanabe Plastics Machinery Co., Ltd. product, "VS-40" (uniaxial extruder with vent of screw diameter 40mm). And melted and kneaded under the condition of a screw rotation speed of 50 rpm and extruded to prepare a pellet-shaped conductive resin composition.

[Manufacturing method of test piece for evaluation]

After drying the pellet-form electroconductive resin composition obtained by said method using the hot air dryer of 110 degreeC for 4 hours, the cylinder set temperature of 300-330 degreeC and mold temperature were carried out using Toshiba Machine Co., Ltd., IS150 type injection molding machine. When molding a molded article for evaluating the molded article appearance and surface resistivity, 100 to 120 ° C. depending on the composition, and at 140 ° C. when molding a molded article for tape peelability evaluation, the molded article appearance, surface resistivity and tape peelability evaluation A plate molded article having a width of 50 mm x 90 mm x 3.2 mmt was injection molded. About the IS0 test piece for the Charpy impact test and the load deflection temperature test, the J50 type injection molding machine manufactured by Nippon Steel Co., Ltd. was used, and the above-mentioned plate-shaped articles were molded under the same temperature condition as the injection molding.

[Examples 1-3 and Comparative Examples 1-4]

The evaluation results performed in the above method are shown in Table 1 below.

The resin compositions of Examples 1 to 3 of the present invention had low odor and had no blockage at the time of injection molding, and were excellent in appearance of the molded article, impact strength, DTUL, surface resistivity, and tape peelability. On the other hand, the resin composition of the comparative example 1 which did not use zeolite had remarkably strong odor, and also fell in impact strength. Moreover, the resin composition of the comparative example 2 which is a composition similar to Example 1 except having used the X zeolite used by the well-known document had a little bad smell, the appearance of the molded article was poor, and the impact strength and tape peelability were also inferior. In addition, the resin composition of the comparative example 3 which is the composition similar to Example 2 except having used the master pellet of stainless steel fiber instead of the stainless steel microfiber (D) has a little bad odor, and from the 135th shot from the start of molding The gate was blocked and molding was impossible, the appearance of the molded article and the tape peelability were lowered, and the impact strength was greatly reduced. Instead of the stainless steel microfibers (D), the resin composition of Comparative Example 4 using carbon black had some odors, the molded article appearance and DTUL were lowered, and the impact strength and tape peelability were also inferior.

Claims (11)

50-200 weight part of stainless steel microfibers (D) with respect to 100 weight part of resin components (C) containing 50-92 weight% of polyphenylene ether (A) and 50-8 weight% of styrene-type resin (B), And 0.1-5.0 weight part of synthetic zeolites (E) represented by following formula (1). _{M 2 / n O · Al 2} O 3 · xSiO 2 · yH 2 O (1) (Wherein M represents an ion-exchangeable monovalent or divalent metal, n represents the valence of the metal, and x represents a number from 10 to 500 in terms of silica coefficient (molar ratio of SiO ₂ / Al ₂ O ₃ ). Y represents the number of 0-7 in the number of crystallized water) The method of claim 1, The conductive resin composition whose polyphenylene ether (A) is a polymer which has a structural unit represented by following formula (2) in a principal chain. [Formula 1]

(In formula, R <_1> represents a C1-C3 lower alkyl group, R <_2> and R <_3> represent a hydrogen atom or a C1-C3 lower alkyl group, respectively.) The method according to claim 1 or 2, The conductive resin composition wherein the styrene resin (B) is polystyrene or impact resistant polystyrene. The method according to any one of claims 1 to 3, The said resin component (C) contains 60-90 weight% of polyphenylene ether (A) and 40-10 weight% of styrene resin (B). The method according to any one of claims 1 to 4, Conductive resin composition whose M in said Formula (1) is sodium. The method according to any one of claims 1 to 5, The conductive resin composition whose silica coefficient x in said Formula (1) is 20-60, and the number y of crystal water is 0-7. The method according to any one of claims 1 to 6, The conductive resin composition wherein the synthetic zeolite (E) is an MFI zeolite. The method according to any one of claims 1 to 7, The conductive resin composition whose average fiber length of the said stainless steel microfiber (D) is 50-500 micrometers, and an average fiber diameter are 1-50 micrometers. The method according to any one of claims 1 to 8, The electrically conductive resin composition formed by mix | blending 0.01-20 weight part of coloring agents (F) with respect to 100 weight part of said resin components (C) further. The molded article formed by shape | molding the electrically conductive resin composition in any one of Claims 1-9. The method of claim 10, A molded article wherein the molded article is a tray for conveying electrical and electronic components.