WO2008018349A1

WO2008018349A1 - Conductive resin composition and molded article obtained by molding the same

Info

Publication number: WO2008018349A1
Application number: PCT/JP2007/065128
Authority: WO
Inventors: Satoshi Hoshino; Zenpei Mizutani
Original assignee: Mitsubishi Engineering-Plastics Corporation
Priority date: 2006-08-08
Filing date: 2007-08-02
Publication date: 2008-02-14
Also published as: CN101495573A; TW200833780A; CN101495573B; KR20090037916A

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

Specification

Conductive resin composition and molded product formed by molding the same

Technical field

[0001] The present invention relates to a novel conductive resin composition, and more specifically, a polyphenylene ether resin composition containing a styrene resin (hereinafter, abbreviated as a modified polyphenylene ether resin S). Conductive resin compositions that reduce odors that occur during melt-kneading and high-temperature heating of molded products, and suppress the adhesion of dust and dust, and storage containers for electric and electronic parts formed by molding the resin compositions, The present invention relates to a molded product such as a transport tray. Background art

[0002] In recent years, electrical / electronic / OA devices have become smaller, lighter, more integrated, and more accurate, and as a result, dust and dust adherence to electrical and electronic parts has been reduced as much as possible! / The demand is increasing. In the first place, if dust or dust adheres to electrical / electronic components, it will cause problems such as poor contact and reading error, so it inherently dislikes the adhesion of dust and dust. The demands are becoming stricter due to higher integration, higher integration, and higher accuracy. For example, wafers used in semiconductors, IC chips, digital cameras, CCD image sensors used in video cameras, solid-state image sensors such as CMOS image sensors, and internal components of hard disks used in computers are the best examples. These electrical and electronic parts are usually manufactured and assembled in a so-called clean room with very little dust and dust, and no dust or dust is deposited here. However, when transporting electrical and electronic parts, it is exposed to the outside air, so the adhesion of dust and dust becomes a problem. In order to avoid this problem, it is required to use resin materials with electrical conductivity for parts for transporting and storing electrical and electronic parts (IC and CCD trays, cases, housings, etc.).

[0003] On the other hand, processes such as production of resin compositions and injection molding are usually performed at high temperatures, for example, 200 to 280 ° C for styrene resins, 260 ° C to 360 ° C for polyphenylene ether, Modified polyphenylene ether resin often melts at a high temperature of 240 to 350 ° C.

Yes Furthermore, molded articles obtained by molding such resin compositions are often exposed to high temperatures during the course of use. For example, if the molded product is a tray used in IC and CCD manufacturing and transportation processes, the slight moisture contained in the IC and CCD, and volatility such as alkali ions, Br ions, and C1 ions In order to degas and remove (bake) impurities, IC and CCD are placed in the tray and heated in a baking room set at a temperature of 130 ° C or higher. If moisture or gas components remain in the IC or CCD, it will cause a fatal defect in the accuracy of the IC and CCD, and this baking process must be heated sufficiently. Recently, the baking temperature tends to rise to 150 ° C or higher in order to improve the reliability of ICs and CCDs.

[0004] In addition, during high-temperature heating such as melt-kneading, molding or baking of molded products, (1) a small amount of odor derived from manufacturing raw materials remaining in the resin, (2) Odor due to thermal decomposition, (3) Odor due to thermal decomposition or vaporization of additives. In addition, there is a problem that such odor damages the resin composition manufacturing chamber, the molding processing chamber, and the surrounding environment. In addition, this odor is brought into a clean room where ventilation is restricted along with molded products such as IC and CCD trays, and there is a problem that it causes a significant discomfort to the assembly operator of electrical and electronic parts. Therefore, a low odor conductive resin composition is required for trays for transporting electrical and electronic parts.

[0005] In order to impart conductivity to the modified polyphenylene ether resin, it is widely used to mix conductive carbon black and metal fibers. Patent Documents 1 and 2 can be exemplified as modified polyphenylene ether resins blended with conductive carbon black, but have the following drawbacks. (1) Contact of molded product · Detachment of carbon black due to wear during friction (so-called “carbon black peeling”) occurs, and the desorbed carbon black is used in IC, CCD chips, wafers, and computers. Attaches to the internal parts of the hard disk and causes malfunction. (2) Odor is generated when the resin composition or molded product is heated to a high temperature. (3) Deterioration of mechanical strength, moldability, and appearance of molded products due to exposure of carbon black. (4) Since only a black resin composition can be obtained, it is impossible to identify molded products by coloring in various hues.

In addition, when metal fibers longer than 1 mm are added to the resin, Dispersion defects are likely to occur, causing conductive noise and gate clogging.

As a conductive resin composition that solves the above-mentioned problems caused by carbon black and poor dispersion of metal fibers, a resin composition containing metal fibers of 1 mm or less is disclosed in Patent Document 3. Even the metal fibers used in Fig. 3 are clogged with long lengths, and the odor problem that occurs when the resin composition or molded product is heated to a high temperature has been solved! / ,.

[0006] For the purpose of solving odor problems, modified polyphenylene ether resin has carbon black and water adsorption capacity under the conditions of pore size 0.8nm or more, temperature 25 ° C / relative humidity 10% / normal pressure. A resin composition (Patent Document 4) containing 20% by weight or more of synthetic zeolite is disclosed. However, with regard to the synthetic zeolite described in Patent Document 4, attention has been paid only to the water adsorption ability! /, Not to the silica coefficient of crystallite and the amount of crystal water! / It is not specifically described. In addition, only examples using hydrophilic zeolite with a low silica coefficient are described!

[0007] Further, Patent Document 5 is an additive for a resin containing, as a main component, an inorganic powder capable of deodorizing and removing odor generated during kneading and molding of a resin composition. As the inorganic powder, it is disclosed to use an aluminosilicate having silica, metal oxide, and alumina in a specific ratio. However, in the resin composition in which the additive for resin specifically described in Patent Document 5 is blended, there is no description regarding the appearance of the molded product and the mechanical strength, and it is also used in the examples. The inorganic powder had a low silica coefficient.

[0008] Patent Document 1: Japanese Patent Laid-Open No. 2-175754

Patent Document 2: JP 2004-263016 A

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

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

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

Disclosure of the invention

Problems to be solved by the invention

[0009] The inventor of the present application further examined the above Patent Document 4 and described in Patent Document 4. When synthetic zeolite with a moisture adsorption capacity of 20% by weight or more is used, silver is generated on the surface of the molded product, resulting in a molded product with a poor appearance, and the problem of carbon black peeling is not solved. Power, ivy.

Further, when the inventor of the present application further examined the resin composition of Patent Document 5, it was found that the problem of peeling off of the inorganic powder could not be solved.

The problem to be solved by the present invention is that it can be colored in a hue other than black without impairing the original properties of the modified polyphenylene ether resin, and the appearance of the molded product is excellent, and the resin is melt-kneaded and molded. It is an object of the present invention to provide a conductive resin composition in which generation of odor is reduced during high-temperature heating such as the above, or during high-temperature heating of a resin molded product, and a molded product using the resin composition.

Means for solving the problem

[0010] As a result of intensive studies to solve the above problems, the present inventors have synthesized a highly hydrophobic silica alumina silicate having a specific shape of metal fiber and a high SiO / Al 2 O molar ratio. It has been found that the above problem can be solved by using zeolite in combination.

That is, stainless microfiber (D) 50 to 200 parts by weight with respect to 100 parts by weight of resin component (C) containing 50 to 92% by weight of polyphenylene ether (A) and 50 to 8% by weight of styrene resin (B). , And a synthetic zeolite (E) represented by the following formula (1) in an amount of 0.;! To 5.0 parts by weight is a resin composition that does not impair the original properties of the modified polyphenylene ether resin. It is possible to remarkably reduce the generation of odors during high-temperature heating such as melt kneading and molding of resin, and during high-temperature heating of resin molded products, coloring other than black is possible, and the appearance of molded products is also extremely excellent The present inventors have found that it is a resin composition and have reached the present invention.

[0011] M 0 -A1 O -xSiO · νΗ O (1)

2 / n 2 3 2 2

(Wherein, M represents a monovalent or divalent metal capable of ion exchange, n represents the valence of the metal, X represents a silica coefficient (a molar ratio of SiO 2 / Al 2 O), and 10 to 500 And y is the number of water of crystallization, indicating a number from 0 to 7.)

The invention's effect

The low-odor conductive resin composition of the present invention is a modified polyphenylene ether resin inherently It is particularly suitable as a material for storage containers for electrical and electronic parts, trays for transportation, and the like because it maintains the above-mentioned characteristics, can be colored, has little dust and dust adhesion, and has stable conductivity. In addition, a resin composition or a molded product using the resin composition can maintain a comfortable working environment even in a clean room with limited ventilation, which generates very little odor when heated at high temperatures. It is extremely suitable for manufacturing molded products such as trays for transporting electrical and electronic parts.

BEST MODE FOR CARRYING OUT THE INVENTION

[0013] Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. In the present specification, a “group” such as an alkyl group may or may not have a substituent unless otherwise specified.

The polyphenylene ether (A) in the present invention is a polymer having an aromatic polyether structure, preferably the following formula (2)

[0014] [Chemical 1]

(In the formula, R is a lower alkyl group having 1 to 3 carbon atoms, and R and R are each a hydrogen atom.

one two Three

Or a lower alkyl group having 1 to 3 carbon atoms. )

A polymer having a structural unit represented by the following formula in its main chain, which may be a homopolymer or a copolymer.

R is preferably a methyl group or an ethyl group.

1

When R and R are lower alkyl groups having 1 to 3 carbon atoms, methyl and ethyl groups are preferred.

twenty three

Good.

Examples of polyphenylene ether (A) include poly (2,6 dimethyl-1,4 phenylene) ether, poly (2,6 dimethyl-1,4 phenylene) ether, and poly (2,6 di). Various kinds of homopolymers such as propinoleyl 1,4 phenylene) ether, poly (2 methyl 6 ethyl 1,4 phenylene) ether, poly (2 methyl-6 propyl 1,4 phenylene) ether, and various 2,6 dialkyls Forces that include copolymers such as phenol / 2,3,6 trialkylphenol copolymers, especially poly (2,6-dimethyl-1,4phenylene) ether, 2,6 dimethylphenol / 2,3,6 trimethyl Phenol copolymers are preferred. Polyphenylene ether containing a molecular component that improves properties such as molecular weight, melt viscosity, and impact strength is also suitable.

[0016] The polyphenylene ether (A) used in the present invention preferably has an intrinsic viscosity at 30 ° C of 0.2 to 0.8 dl / g as measured in chloroform. A force of 3 to 0.6 dl / g is preferable. When the intrinsic viscosity is 0.2 dl / g or more, the mechanical strength of the resin composition tends to be improved, and when it is 0.8 dl / g or less, the fluidity is improved and the molding process is increased. It tends to be easier.

[0017] The styrene resin (B) used in the present invention includes a styrene monomer polymer, a copolymer of a styrene monomer and another copolymerizable monomer, and a styrene resin. Examples thereof include graft copolymers.

[0018] Examples of the styrene monomer include styrene, α-methylstyrene, ρmethylstyrene, and preferably styrene. Examples of monomers that can be copolymerized with styrenic monomers include cyanuric butyl monomers such as acrylonitrile and methacrylonitrile, methyl acrylate, ethyl acrylate, propyl acrylate, methyl methacrylate, Examples include (meth) acrylic acid alkyl ester monomers such as methacrylic acid methacrylate, maleimide, Ν-phenylmaleimide, and the like, preferably cyanuric butyl monomer and (meth) acrylic acid alkyl ester monomer. It is done.

Examples of the copolymer of the styrene monomer and other copolymerizable monomers include styrene 'acrylonitrile resin (AS resin) and the like, and examples of the styrene graft copolymer include , Impact-resistant polystyrene (HIPS resin), acrylonitrile / butadiene / styrene resin (ABS resin), AES resin in which the butadiene of the ABS resin is replaced with ethylene propyne rubber, acrylonitrile / acrylate / styrene resin (AAS resin), etc. Is mentioned. Styrene copolymers can be produced by emulsion polymerization, solution polymerization, suspension, etc. Well-known methods, such as a turbid polymerization method or a block polymerization method, are mentioned.

The styrenic resin (B) is preferable in terms of compatibility with polystyrene and impact-resistant polystyrene strength polyphenylene ether. Particularly when impact resistance is required, impact-resistant polystyrene is more preferable.

[0019] The resin component (C) in the present invention contains 50 to 92% by weight of the polyphenylene ether (A) and 50 to 8% by weight of the styrene resin (8). Preferably, the polyphenylene ether (A) is 60 to 90% by weight and the styrene resin (B) is 40 to 40%; more preferably, the polyphenylene ether (A) is 70 to 90% by weight. it is intended to include styrene-based resin (B) 30-10 weight ^_0/0. If the polyphenylene ether (A) is less than 50% by weight, the stagnation temperature and mechanical strength tend to decrease, and if it exceeds 92% by weight, the fluidity tends to decrease and the molding process tends to become complicated. It is not preferable.

[0020] The resin component (C) in the present invention is preferably further blended with a styrene elastomer in order to improve impact strength. The styrenic elastomer that is preferably blended in the present invention has at least one heavy polymer selected from the group consisting of polybutadiene, polyisoprene, and hydrogenated products thereof, in which the hard segment is composed of a styrene polymer. Block copolymer composed of polymer, specifically SBS (styrene / butadiene), SEBS (styrene / ethylene / butylene / styrene block copolymer: hydrogenated SBS), SEPS (styrene / ethylene / propylene / Styrene block copolymer: hydrogenated product of SIS) and the like, and SEBS is particularly preferable.

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

The number average molecular weight of the styrenic elastomer is preferably from 20,000 to 180,000, more preferably from 30,000 to 160,000, and even more preferably from 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 are excellent, and the appearance of the molded product obtained from the resin composition is also excellent. The ability to make S Further, it is preferable that the number average molecular weight is 180,000 or less because the fluidity of the finally obtained resin composition is improved and the molding process becomes easy.

[0021] The amount of the styrene-based elastomer scratch, in the resin component (C),;! ~ 25 weight ^_0/0, preferably 3 to 20 wt%, more preferably 5 to; blended so that 15 wt% To do. The impact strength tends to be further improved by adding 1% by weight or more of the styrene elastomer. Moreover, when the blending amount of the styrene elastomer is 25% by weight or less, the rigidity and load stagnation temperature of the resin composition tend to be improved, which is preferable.

Furthermore, the resin component (C) used in the present invention may contain other resin components without departing from the spirit of the present invention. In this case, the blending amount is usually 50% by weight or less of the resin component (C).

[0022] In the present invention, a stainless microphone fiber (D) is blended mainly for the purpose of imparting conductivity to the resin composition. The type of stainless steel used as a raw material for the stainless microfiber (D) used in the present invention is not limited, but SU S304, SUS316, SUS403, and their mixture power are particularly preferable in the JIS regulations.

The average fiber length of the stainless microfiber (D) is preferably 50 to 500 μm, more preferably 100 to 300 111. When the average fiber length is 50 m or more, the conductive effect tends to be improved. By setting the average fiber length to 500 m or less, poor dispersion due to entanglement between fibers occurs, and there are variations in conductivity and gates during molding. Clogging is likely to occur, and the mechanical strength tends to improve.

The average fiber diameter of the stainless microfiber (D) is preferably 1 to 50 111, more preferably 10 to 30 111, and particularly preferably 10 to 20 111. When the average fiber diameter is set to m or more, the fibers are difficult to break. When the average fiber diameter is set to 50 m or less, the conductive effect is improved and the appearance tends to be improved. Note that the average fiber length and average fiber diameter of the stainless microfiber in the present invention are obtained by dispersing the raw stainless steel microfiber on a slide glass, observing with a microscope and taking a photograph, and It is the number average of the values obtained by measuring the fiber length and fiber diameter of 2000 stainless microfibers using analysis software (“Image-Pro Plus” manufactured by Planetron). The specific gravity of the stainless microfiber (D) is preferably 7 · 7 to 8 · 0. The stainless microfiber (D) used in the present invention can be treated with a surface treatment agent such as a coupling agent used as a glass fiber surface treatment agent.

Stainless steel microfiber (D) of the present invention has a good surface appearance and less drop-out compared to conductive carbon black or the like conventionally used for imparting conductivity, because it has less bleed-out to the surface of the molded product. . In addition, since the volume ratio with respect to the blending amount is small, the dispersibility in the resin composition is also good, and there is no variation in conductivity, uneven color of the molded product, and mechanical strength does not decrease due to poor dispersion. . In the present invention, the above performance can be exhibited more effectively by using a stainless microfiber (D) having a short average fiber length of about 100 to 300 111.

[0023] The amount of stainless microfiber (D) is 50 to 100 parts by weight of resin component (C).

200 parts by weight, preferably 60 to 50 parts by weight, more preferably 60 to 20 parts by weight. When the blending amount is 50 parts by weight or more, the surface resistance value is greatly reduced and the conductive effect tends to be improved. Further, when the content is 200 parts by weight or less, the specific gravity tends to decrease and the mechanical strength tends to improve.

[0024] In the present invention, the main purpose is to reduce the odor derived from the residual production raw material, the odor due to the thermal decomposition of the resin, the odor due to the thermal decomposition or vaporization of the additive, etc. generated from the resin composition during high-temperature heating. And synthetic zeolite (ライト). The synthetic zeolite used in the present invention is generally an aluminosilicate having a three-dimensional skeleton structure and is represented by the following formula (1).

[0025] M 0 -A1 O -xSiO · νΗ O (1)

2 / n 2 3 2 2

(Wherein, M represents a monovalent or divalent metal capable of ion exchange, n represents the valence of the metal, and X represents a number of 10 to 500 in terms of silica coefficient (SiO 2 / Al 2 O molar ratio). And y is the number of water of crystallization and represents a number from 0 to 7.)

[0026] Zeolite includes natural zeolite and synthetic zeolite, and synthetic zeolite has a low silica coefficient (less than 10) hydrophilic zeolite (for example, A-type zeolite, X-type zeolite, Y-type zeolite), The force S having a high silica coefficient (10 or more) hydrophobic zeolite (for example, MFI type zeolite) S, the synthetic zeolite (E) used in the present invention is a hydrophobic zeolite. Of these, MFI type synthetic zeolite is preferred because of its availability from the factory. The hydrophobic MFI-type synthetic zeolite has a three-dimensional network structure in which the pore entrance is formed by a 10-membered oxygen ring and consists of linear pores and zigzag pores intersecting them. For example, an oval shape having an effective pore diameter of 5 to 6 A, a pore volume of 0.15 to 25 mL Zg, and a specific surface area of 300 to 550 m ² / g is preferred. An oval shape having a pore volume of 0.15—0.25 mL / g and a specific surface area of 300 to 450 m ² / g is more preferable.

[0027] The synthetic zeolite (E) used in the present invention needs to be represented by the above formula (1), and the silica coefficient X force is more preferably 20 to 60, and further preferably 30 to 60. It is. More preferably, M in formula (1) is sodium, preferably sodium, potassium or calcium! /. The y value in equation (1) is low! /, Better! /.

Furthermore, the synthetic zeolite (E) used in the present invention has a water adsorption capacity of preferably less than 20% by weight, more preferably less than 15% by weight under the conditions of temperature 25 ° C./relative humidity 10% / normal pressure. The synthetic zeolite is full, more preferably less than 10% by weight. In particular, a synthetic zeolite having a silica coefficient X of 20 to 60 and a water adsorption capacity of less than 10% by weight at a temperature of 25 ° C./relative humidity of 10% / atmospheric pressure, represented by the above formula (1), Molded products obtained from such low odor resin compositions formulated with such synthetic zeolite, which has high heat resistance and hydrophobicity, have no appearance of silver and have a very good appearance! / It also has a characteristic.

The average primary particle size of the synthetic zeolite (E) according to the present invention is preferably 0.;! To 20 m, more preferably 0.2 to 10 mm, and further preferably 0.5 to 5 m. 〃M. When the average primary particle size of synthetic zeolite (E) is 0.1 am or more, the melt viscosity of the resin composition tends to be low, and when it is 20 inches or more, the rough surface of the molded product is not noticeable. It is preferable because the appearance tends to be improved.

[0028] The blending amount of the synthetic zeolite (E) is from 0.;! To 5.0 parts by weight, and preferably from 0.2 to 3.0 parts by weight, based on 100 parts by weight of the resin component (C). If the blending amount is less than 0.1 parts by weight, the odor reducing effect is small. Even if the blending amount exceeds 5.0 parts by weight, no further odor reducing effect can be expected, and the mechanical strength also decreases. There's a problem.

[0029] In addition to the above components, the low odor conductive resin composition of the present invention includes a face as necessary. , Coloring agents such as dyes, dyes, aliphatic carboxylic acids, aliphatic carboxylic esters, polyolefin waxes, release agents such as silicone oils, stabilizers such as hindered phenolic compounds, phosphorus compounds and zinc oxide Flame retardants such as phosphate esters and condensed phosphate esters, UV absorbers such as hindered amines, benzotriazoles, benzophenones, and epoxys, antioxidants, lubricants, plasticizers, antistatic agents, and slidability improvers , Additives such as compatibilizers, difluoroethylene polymer, tetrafluoroethylene polymer, tetrafluoroethylene-hexafluoropropylene copolymer, ethylene-based that does not contain tetrafluoroethylene and fluorine Fluorine-based resin, glass fiber, glass flake, carbon fiber, etc. May be blended reinforcing fillers metal fiber or the like other than stainless steel microfibers, or potassium titanate, aluminum borate, whiskers and calcium Kei acid, My force, talc, an inorganic filler clay. The blending method of these additives can be suitably carried out by a conventionally known method that makes use of these characteristics.

In the present invention, a colorant (F) can be added. In the conventional conductive resin composition, carbon black has been employed to impart conductivity, so that only a black resin composition can be obtained in many cases. However, in the present invention, the electroconductivity can be imparted without using the electroconductive carbon black, so that it can be colored freely. Examples of the colorant (F) in the present invention include dyes, inorganic pigments, and organic pigments generally used for thermoplastic resins.

Examples of the dye include azo dyes, anthraquinone dyes, phthalocyanine dyes, indigo dyes, diphenylmethane dyes, atalidine dyes, cyanine dyes, nitro dyes, and niggincin. Inorganic pigments include oxide pigments such as titanium oxide, red pepper and cobalt blue, hydroxide pigments such as alumina white, sulfide pigments such as zinc sulfide and cadmium yellow, silicate pigments such as white carbon and talc, and carbon black. Etc. Examples of organic pigments include nitro pigments, azo pigments, phthalocyanine pigments, and condensed polycyclic pigments. Of these, inorganic pigments are preferred because they are difficult to bleed out to the surface of the molded product. In addition, for the purpose of improving handleability during extrusion, the colorant is a thermoplastic resin such as a polyethylene ether resin, a polystyrene resin, a polycarbonate resin, or an acrylic resin. You can also use a base resin and a base resin.

[0031] The blending amount of the colorant (F) is preferably 0.0;! To 20 parts by weight with respect to 100 parts by weight of the resin component (C). More preferably, it is! In addition, inorganic pigments such as titanium oxide may be used for purposes other than coloring (for example, imparting light-shielding properties). In such cases, the blending amount is usually 5 parts per 100 parts by weight of the resin component (C). ~ 20 parts by weight, preferably 5 ~; 15 parts by weight. Two or more of these colorants may be used in combination.

[0032] Examples of the stabilizer in the present invention include hindered phenol compounds, phosphorus compounds, and zinc oxide.

Specific examples of the hindered phenol compounds include n-octadecyl-3- (3,5-ditertbutyl-4-hydroxyphenyl) propionate, 1,6-hexanediorebis [3- (3,5-ditertbutylbutyl-4 -Hydroxyphenol) propionate], pentaerythritol tetrakis [3- (3,5-ditertbutyl-4-hydroxyphenol) propionate], 2,6 ditertbutyl-4-methylphenol, 3,9bis [1,1 dimethyl-2- {β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2, 4, 8, 10 tetraoxaspiro [5,5] undecane, triethylene glycol bis [3- (3-tert-butyl-5 —Methyl-4-hydroxyphenol) propionate], 3, 5-di-tert-butyl-4-hydroxybenzyl Shonate Jetinore Estenole, 1, 3, 5 Trimethinole 2, 4, 6 Tris (3,5 Di tert-butyl-4-hydroxybenzyl) benzene, 2, 2 Thiodiethylenebis [3- (3, 5- Di-tert-butyl-4-hydroxyphenyl) propionate], tris- (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, N, N'hexamethylene bis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamate Mid) and the like. Among these, n-octadecyl-3- (3,5-ditertbutyl-4-hydroxyphenenole) propionate, 1,6-hexanediol bis [3- (3,5-tertbutynole 4-hydroxyphenenole) propionate], 2 , 6 Di-tert-butyl-4-methylphenol, 3, 9 Bis [1,1--dimethylolate 2-- {/ 3- (3-tert-butyl 4-hydroxy-5-methylphenol) propionyloxy} ethyl] 2, 4, 8 10 Tetraoxaspiro [5,5] undecane is preferred. [0033] As the phosphorus compound, for example, a phosphonite compound or a phosphite compound is preferably used.

Examples of the phosphonite compound include tetrakis (2,4 ditertbutylphenyl) -4,4′-biphenyl dirange phosphonite, tetrakis (2,5 ditertbutylphenyl) -4,4′-biphenyldirange phosphonite, tetrakis ( 2, 3, 4 Trimethylphenyl) 1, 4, 4'-biphenyl dirange phosphonite, tetrakis (2, 3 dimethyl-5 ethenyl phenyl) 4, 4'-biphenyl dirange phosphonite, tetrakis (2, 6 di tert butyl-5) 4, 4'-biphenyl dirange phosphonite, tetrakis (2, 3, 4 tributyl phenyl) 4, 4'-biphenyl dirange phosphonite, tetrakis (2, 4, 6 tri tert-butyl phenyl) 4, 4'-biphenyl Range phosphonites and the like are mentioned. Among them, tetrakis (2,4 di tert butylphenyl) 4,4′-biphenyl dirange phosphonite is preferable. Examples of sphite compounds include tris (2,4 di tert butylphenyl) phosphite, bis (2,4 di tert butylphenyl) pentaerythritol diphosphite, bis (2,6 di tert butyl-4-methylphenyl) pentaerythritol diphosphite. Spite, 2, 2 Methylenebis (4,6 di tert butylphenyl) octyl phosphite, 4, 4 'Butylidene bis (3-methyl 6-tert butylphenyl ditridecyl) phosphite, 1, 1, 3—Tris (2 —Methyl 4-ditridecylphosphia I, 15-tert-butylphenyl) butane, tris (noyulpheninole) phosphite, 4,4′-isopropylidenebis (phenyldialkylphosphite) and the like. 2,4 di-tertbutylbutyl) phosphite, 2,2 methylenebis (4,6 ditertbutylbutyl) Enyl) octyl phosphate, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol 1, mono-diphosphite and the like are preferred.

[0034] As zinc oxide, for example, an average particle diameter of 0.02 to 1 μm is preferable, and an average particle diameter of 0.08 to 0.8 m is more preferable.

Among these stabilizers, zinc oxide is preferable because it does not easily cause mold disposition and discoloration is difficult.

[0035] The amount of the stabilizer is preferably 0.01 to 5 parts by weight per 100 parts by weight of the resin component (C). More preferably, it is 0.05 to 3 parts by weight. If the blending amount is 0.01 parts by weight or more, the effect as a stabilizer can be sufficiently exerted, and if it is 5 parts by weight or less, the mechanical strength is reduced and mold deposits are generated during molding. Can be deterred. Two or more of these stabilizers may be used in combination.

[0036] Examples of the release agent in the present invention include aliphatic carboxylic acid, aliphatic carboxylic acid ester, polyolefin wax, silicone oil, and the like.

Examples of the aliphatic carboxylic acid include saturated or unsaturated aliphatic monocarboxylic acid, dicarboxylic acid, and tricarboxylic acid. Here, the aliphatic carboxylic acid includes alicyclic carboxylic acid. Of these, preferred aliphatic carboxylic acids are mono- or dicarboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monocarboxylic acids having 6 to 36 carbon atoms are more preferred. Specific examples of such aliphatic carboxylic acids include noremitic acid, stearic acid, valeric acid, caproic acid, strong puric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, melicic acid, Examples thereof include tetratriacontanoic acid, montanic acid, dartaric acid, adipic acid, and azelaic acid.

[0037] As the aliphatic carboxylic acid component constituting the aliphatic carboxylic acid ester, the same aliphatic carboxylic acid as that described above can be used. On the other hand, examples of the alcohol component constituting the aliphatic carboxylic acid ester include saturated or unsaturated monohydric alcohols and saturated or unsaturated polyhydric alcohols. These alcohols may have a substituent such as a fluorine atom or an aryl group. Of these alcohols, monovalent or polyhydric saturated alcohols having 30 or less carbon atoms are preferred, and aliphatic saturated monohydric alcohols or polyhydric alcohols having 30 or less carbon atoms are preferred. Here, the aliphatic alcohol includes alicyclic alcohol.

[0038] Specific examples of these alcohols include octanol, decanol, dodecanol, stearino oleanoreconole, beheninoleanoreconole, ethyleneglycolole, diethyleneglycolole, glycerin, pentaerythritole, 2, 2 —The ability to list dihydroxypenole folanol propanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol, etc. These aliphatic carboxylic acid esters are mixtures of a plurality of compounds that may contain aliphatic carboxylic acids and / or alcohols as impurities. May be.

[0039] Specific examples of the aliphatic carboxylic acid ester include beeswax (mixture containing myristyl palmitate as a main component), stearyl stearate, behenyl behenate, octyldodecyl behenate, glycerin monopalmitate, glycerin Monostearate, Glycerol distearate, Glycerin tristearate, Pentaerythritol monopalmitate, Pentaerythritol Monoremonosterate, Pentaerythritonorestearate, Pentaerythritol retristearate, Pentaerythritol tetrastearate Can be mentioned.

[0040] The polyolefin waxes include olefin homopolymers and copolymers. Examples of the homopolymer of olefin include polyethylene wax, polypropylene wax and the like, partial oxides thereof, and mixtures thereof. The copolymers of olefin include α, such as ethylene, propylene, 1-butene, 1-hexene, 1-decene, 2-methylbutene 1, 3-methylbutene 1, 3-methylpentene 1, 4-methylpentene 1, etc. —Copolymers such as olefins, monomers copolymerizable with these olefins, such as unsaturated carboxylic acids or their anhydrides [maleic anhydride, (meth) acrylic acid, etc.], (meth) acrylic acid esters [( And a copolymer with a polymerizable monomer such as (meth) acrylic acid alkyl ester having 1 to 6 carbon atoms such as methyl (meth) acrylate and ethyl (meth) acrylate. In addition, these copolymers include random copolymers, block copolymers, and graft copolymers. 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. The polyolefin wax may have a linear or branched structure.

Yes

[0041] Examples of the silicone oil include those composed of polydimethylsiloxane, and some or all of the methyl groups of polydimethylsiloxane are phenyl groups, hydrogen atoms, alkyl groups having 2 or more carbon atoms, halogenated phenyl groups, fluoroester groups. Silicone-substituted silicone oil, epoxy-modified silicone oil having an epoxy group, amino-modified silicone oil having an amino group, alcohol-modified silicone oil having an alcoholic hydroxyl group, polyether-modified silicone oil having a polyether structure, and the like. , 2 types You may use together.

[0042] The compounding amount of the mold release agent is preferably 0.01 to 10 parts by weight, more preferably 0.0 to 6 parts by weight with respect to 100 parts by weight of the resin component (C). More preferably 3 to 5 parts by weight. When the blending amount is 0.01 parts by weight or more, the mold release effect is more exerted, and when it is immediately 10 parts by weight or less, problems such as heat resistance, mold contamination, and poor plasticization occur. .

[0043] As a method for obtaining the conductive resin composition of the present invention, for example, (1) various kneaders such as a uniaxial and multi-axial kneader, a Banbury mixer, a roll, a Brabender plastogram, etc. A method of melt-kneading the above-mentioned components and additives added as necessary; and (2) after previously kneading a part of the above-mentioned components and additives added as needed, with other components In addition, a method of further kneading (including a method using a masterbatch), (3) Add additives that are added as necessary to carbonize an appropriate solvent such as hexane, heptane, benzene, toluene, xylene, etc. Examples thereof include a solution mixing method in which the resin component (C) is mixed with hydrogen or a derivative thereof or mixed with the resin component (C) in a suspended state. The melt kneading method (1) or (2) is preferable from the industrial cost, but is not limited thereto. In melt kneading, it is preferable to use a single-screw or twin-screw extruder.

[0044] As a method of molding a molded product formed using the conductive resin composition of the present invention, for example, a storage container or a transfer tray for electrical and electronic parts, an injection molding method is used because of its good productivity. Although it is often used, molding methods commonly used for thermoplastic resins, such as hollow molding, extrusion molding, thermoforming from sheet-shaped molded products, and rotational molding, are also applicable. it can.

Molded products molded using the conductive resin composition of the present invention include (for example, force S including storage containers or trays for transporting electrical and electronic parts such as IC and CCD trays, cases, and housings, The conductive resin composition of the present invention is suitable for IC and CCD trays used at high temperatures such as baking.

[0045] The Charpy impact strength of the resin composition of the present invention is preferably 2 Okj / m ² or more when measured by the method described below. The load stagnation temperature of the resin composition of the present invention is preferably 155 ° C. or higher when measured by the method described later.

Example Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded. Evaluation of the resin composition and the molded product in Examples and Comparative Examples was performed as follows.

[0047] (1) Odor A: During melting and kneading of the resin composition performed under the manufacturing conditions described later, five people smelled at a location 50 cm away from the die of the twin-screw extruder (screw diameter 30 mm). The following points were used as the evaluation points, and the total points of all members were used as the evaluation points.

Odor B: An ISO test piece for Charpy impact test obtained under the molding conditions described below was placed in a 300 ml stoppered Erlenmeyer flask, heated at 140 ° C for 3 hours, and five people smelled the odor and evaluated it according to the following criteria. A score was assigned, and the total score of all members was used as the evaluation score.

Evaluation points Evaluation criteria

1 point Very faint smell

2 point Smell

3 points

4 points Strong smell

5 points Very strong odor

[0048] (2) Gate occlusion: Thickness 1. Omm, diameter 50mm In the center of a disk with a mold with a gate diameter of 0.7mm, gate land 2.0mm, cylinder set temperature 290 ~ 330

500 shots of continuous injection molding were performed under the conditions of ° C, mold temperature 120 ° C, and molding cycle 30 seconds, and the power at which gate clogging occurred in many yachts was investigated. Those that did not clog even after 500 shots are displayed in Table 1 as “> 500”.

[0049] (3) Appearance of molded product: Molded product with excellent appearance by visually observing the occurrence of silver, flow mark, etc. in a square plate molded product of 50mm x 90mm x 3.2mmt obtained under the molding conditions described later In order from the first, the following three grades were evaluated: ○, △, and X.

○: No appearance defects such as silver and flow mark!

Δ: Some appearance defects such as silver and flow mark are seen.

X: Appearance defects such as silver and flow mark are conspicuous.

[0050] (4) Charpy impact strength: Measured by 5 pieces at 23 ° C according to IS0527 standard using Char specimens for Charpy impact test obtained under the molding conditions described below. One impact strength (hereinafter abbreviated as impact strength) is shown.

[0051] (5) Load stagnation temperature: In accordance with IS075 standard, using the ISO test piece for load stagnation temperature test obtained under the molding conditions described below. 1. Under the condition of 82 MPa, the deflection temperature under load (hereinafter referred to as DTUL) (Abbreviation) was measured.

[0052] (6) Surface resistivity: 50mm x 90mm x 3.2mmt square plate molded product obtained under the molding conditions described later, and placed at any three locations using Loresta or Hiresta of Mitsubishi Chemical Corporation. And measured. Hiresta was used when the surface resistivity was 10 ⁴ Ω or higher, and Loresta was used when the surface resistivity was lower.

[0053] (7) Tape peelability: 50 mm × 90 mm × 3.2 mmt square plate molded product obtained under the molding conditions described later, and the product name “Sero Tape (registered trademark)” manufactured by Nichiban Co., Ltd. on the molded product surface. CT4 05A-18 ”was affixed, and the peeled surface of the molded product when it was peeled off was visually observed and evaluated in the following three grades: ○, △, and X. It can be judged that the less the peeling, the less the stainless microfiber and carbon black peel off.

◯: Even if the tape is peeled off after applying cellophane and rubbed with force, there is no peeling of the molded product surface.

Δ: Peeling occurs on the surface of the molded article when the tape is peeled off after applying cellophane and rubbing with force.

X: Peeling occurs on the surface of the molded product even if a cellophane tape is applied and lightly rubbed.

[0054] [Raw materials]

The following raw materials were prepared.

(1) Poly (2, 6 dimethyl-1, 4 phenylene) ether resin: Mitsubishi Engineering Plastics Co., Ltd., trade name “PX100F”, intrinsic viscosity 0.38dl / g (at 30 ° C in black mouth form) Measurement) (hereinafter abbreviated as “PPE”)

(2) Styrene resin: High impact polystyrene: manufactured by Toyo Styrol Co., Ltd., trade name “H 485”, weight average molecular weight 200,000, MFR 3.2 g / 10 min (hereinafter abbreviated as “HIPS”)

[0055] (3-1) Stainless steel microfiber: manufactured by JFE Techno Research Co., Ltd., trade name "SMF-7 08AE", average fiber length 150 111, average fiber diameter 15 m, specific gravity 7.9 (hereinafter "3 ^ Abbreviated ^ '') (3- 2) (For comparative example) Stainless steel: Master pellet of stainless steel, Toyo Ink Manufacturing Co., Ltd., trade name “Rioconduct”, 8 m diameter stainless steel fiber converged with polyester, pellet length 4 mm Cut, stainless steel fiber content 75% by weight (hereinafter abbreviated as “SU S”)

(3-3) Carbon Black: Ketjen 'Black' International, trade name “Ketjen Black EC”, average particle size 30 m (hereinafter abbreviated as “CB”)

[0056] (4 1) MFI type synthetic high silica zeolite: manufactured by Mizusawa Chemical Industry Co., Ltd., trade name “Mizu-Force Sieves EX-122”, M in the above formula (1) is sodium, and n is 1. The silica coefficient x = 33 and the number of crystal waters y = 0-7. In addition, it has an oval shape with an effective pore size of 5 to 6 A, a pore volume of 0.15 to 0.25 mL / g, a specific surface area of 300 to 450 m ² / g, an average primary particle size of 2.0 μm, and a temperature of 25 ° Moisture adsorption capacity under conditions of C / relative humidity 10% / atmospheric pressure is 7% by weight (hereinafter abbreviated as “M zeolite”)

(4-2) (For comparative example) X-type zeolite: manufactured by Nippon Chemical Industry Co., Ltd., trade name “Zeostar NX—110P”, silica coefficient x = 2.6, effective pore size 9A, average primary particle size 3 111, water adsorption capacity under the conditions of temperature 25 ° C / relative humidity 10% / normal pressure 25% by weight (hereinafter abbreviated as “X zeolite”)

[0057] (5) Mold release agent: polyethylene wax, manufactured by Sanyo Chemical Industries, trade name “Sunwax 151P”, density 0.93 g / ml, weight average molecular weight 2,000 (hereinafter abbreviated as “release agent”)

(6) Stabilizer: Zinc oxide (reagent grade 1), manufactured by Honjo Chemical Co. (hereinafter abbreviated as “stabilizer”)

(7) Colorant: Red inorganic pigment, manufactured by Toda Kogyo Co., Ltd., trade name `` 140ED ''

[0058] [Method for producing resin composition]

A composition prepared by adjusting the above raw materials with the blending ratios shown in Table 1 using a “VS-40” (single screw extruder with a 40 mm screw diameter) manufactured by Tanabe Plastics Machinery Co., Ltd. It was melted and kneaded under conditions of 270 to 320 ° C. and a screw rotation speed of 50 rpm, and extruded to produce a pellet-shaped conductive resin composition.

[Method for producing test specimen for evaluation]

The pellet-shaped conductive resin composition obtained by the above method was dried for 4 hours using a hot air dryer at a temperature of 110 ° C., and then the cylinder was made using a IS150 type injection molding machine manufactured by Toshiba Machine Co., Ltd. Set the mold temperature to 300 to 330 ° C, and the mold temperature to 100 to 120 ° C depending on the composition when molding the molded product appearance and surface resistivity evaluation. In the case of molding, a square plate molded product of 50 mm × 90 mm × 3.2 mmt for evaluation of molded product appearance, surface resistivity and tape peelability was injection molded at 140 ° C. ISO specimens for Charpy impact test and load stagnation temperature test were molded under the same temperature conditions as the above-mentioned square plate molded products were injection molded using a J50 injection molding machine manufactured by Nippon Steel Works. did.

[0059] [Examples;! To 3, Comparative examples;! To 4]

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

The resin compositions of Examples of the present invention;! To 3 were low in odor, did not clog the gate during injection molding, and were excellent in appearance of molded product, impact strength, DTUL, surface resistivity, and tape peelability. In contrast, the resin composition of Comparative Example 1 which did not use zeolite was extremely strong in odor and inferior in impact strength. In addition, the resin composition of Comparative Example 2 having the same composition as Example 1 except that X zeolite used in the publicly known literature has a slight odor, the appearance of the molded product is poor, impact strength and tape The peelability was also poor. In addition, the resin composition of Comparative Example 3 having the same composition as Example 2 except that stainless steel master pellets were used in place of the stainless microfiber (D) was slightly inferior in odor and molded. At the 135th shot from the start, the gate closed and molding was impossible, and the appearance of the molded product and tape peelability were reduced, and the impact strength was greatly inferior. The resin composition of Comparative Example 4 using carbon black instead of stainless microfiber (D) had a slight odor, the appearance of the molded product and DTUL were lowered, and the impact strength and tape peelability were greatly inferior.

[0060] [Table 1]

Claims

The scope of the claims

[1] to Porifue two ether (A) fifty to ninety-two wt% and a styrene-based resin (B) fifty to eight weight ^_0/0 including a resin component (C) 100 parts by weight, stainless microfiber (D) 50 A conductive resin composition comprising -200 parts by weight and 0.; -5.0 parts by weight of synthetic zeolite (E) represented by the following formula (1).

M 0 -A1 O -xSiO νΗ O (1)

2 / n 2 3 2 2

[2] The conductive resin composition according to claim 1, wherein the polyphenylene ether (A) is a polymer having a structural unit represented by the following formula (2) in the main chain.

[Chemical 1]

one two Three

Or a lower alkyl group having 1 to 3 carbon atoms. )

[3] The styrenic resin (B) 1 polystyrene or high-impact polystyrene.

3. The conductive resin composition according to 1 or 2.

[4] The resin component (C) comprises 60 to 90% by weight of polyphenylene ether (A) and a styrene resin.

The conductive resin composition according to any one of claims 1 to 3, comprising (B) 40 to 10% by weight.

[5] The conductive resin composition according to any one of claims 1 to 4, wherein M in the formula (1) is sodium.

[6] The conductive resin composition according to [1], wherein the silica coefficient X in the formula (1) is 20 to 60, and the number y of crystal water is 0 to 7; . The conductive resin composition according to any one of claims 1 to 6, wherein the synthetic zeolite (E) is MFI-type zeolite.

The conductive resin composition according to any one of claims 1 to 7, wherein the stainless microfiber (D) has an average fiber length of 50 to 500 Hm and an average fiber diameter of 1 to 50111. The conductive material according to claim 1, further comprising 0.0; 20 to 20 parts by weight of a colorant (F) based on 100 parts by weight of the resin component (C). Resin composition.

A molded article formed by molding the conductive resin composition according to claim 1, whichever force of claim 1. 11. The molded article according to claim 10, wherein the molded article is a tray for transporting electrical and electronic parts.