WO2019045030A1 - Electroconductive resin composition - Google Patents

Electroconductive resin composition Download PDF

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Publication number
WO2019045030A1
WO2019045030A1 PCT/JP2018/032286 JP2018032286W WO2019045030A1 WO 2019045030 A1 WO2019045030 A1 WO 2019045030A1 JP 2018032286 W JP2018032286 W JP 2018032286W WO 2019045030 A1 WO2019045030 A1 WO 2019045030A1
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WO
WIPO (PCT)
Prior art keywords
copolymer
vinyl compound
ethylene
aromatic vinyl
aromatic
Prior art date
Application number
PCT/JP2018/032286
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French (fr)
Japanese (ja)
Inventor
勝 長谷川
雄志 熊谷
荒井　亨
Original Assignee
デンカ株式会社
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Publication date
Application filed by デンカ株式会社 filed Critical デンカ株式会社
Priority to JP2019539652A priority Critical patent/JP7158388B2/en
Publication of WO2019045030A1 publication Critical patent/WO2019045030A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/02—Physical, chemical or physicochemical properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/06—Polystyrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/06—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to homopolymers or copolymers of aliphatic hydrocarbons containing only one carbon-to-carbon double bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports

Definitions

  • the present invention relates to a conductive resin composition, and the conductive resin composition can be suitably used, for example, for packaging electronic components.
  • Packaging containers for electronic parts such as ICs include injection trays, vacuum formed trays, magazines, embossed carrier tapes, cover tapes and the like.
  • the conductive resin The composition is used.
  • a conductive resin composition what consists of a thermoplastic resin and a conductive filler is known.
  • thermoplastic resin polyvinyl chloride resin, polypropylene resin, polyethylene terephthalate resin, polystyrene resin and ABS resin are used, and for heat resistance at 100 ° C. or higher, polyphenylene ether resin, polycarbonate resin, etc. are used. ing.
  • the present invention solves the above-mentioned drawbacks, and a conductive resin composition comprising at least one thermoplastic resin selected from polystyrene resins and ABS resins and carbon black, the conductive resin composition comprising A conductive resin in which contamination of IC and the like caused by detachment of carbon black and the like due to abrasion at the time of contact with an IC and the like is remarkably reduced while maintaining mechanical properties as a resin by containing a cross copolymer. It is an object of the present invention to provide a composition.
  • Composition [2] The conductive resin composition according to [1], wherein the thermoplastic resin is one or more selected from a polystyrene resin and an ABS resin.
  • the cross copolymer is a copolymer having an ethylene-aromatic vinyl compound-aromatic polyene copolymer chain and an aromatic vinyl compound polymer chain, and is an ethylene-aromatic vinyl compound-aromatic polyene
  • the content of the aromatic vinyl compound monomer unit of the ethylene-aromatic vinyl compound-aromatic polyene copolymer chain is 5 mol% or more and 30 mol% or less, and the content of the aromatic polyene monomer unit is 0.
  • the weight average molecular weight of the ethylene-aromatic vinyl compound-aromatic polyene copolymer chain is 50,000 or more and 300,000 or less, and the molecular weight distribution (Mw / Mn) is 1.8 or more and 6 or less.
  • the content of the ethylene-aromatic vinyl compound-aromatic polyene copolymer chain contained in the cross copolymer is in the range of 50% by mass to 95% by mass.
  • the conductive resin composition of the present invention exhibits favorable mechanical properties and molding processability, and further, is very suitable as an electronic component packaging container as a sheet, for example, in that there is very little detachment of carbon black due to contact or friction. It can be used.
  • the present invention is a conductive resin containing 5 to 60 parts by mass of carbon black and 10 to 100 parts by mass of a cross copolymer with respect to 100 parts by mass of a thermoplastic resin and having a surface resistivity of 10 2 to 10 10 ⁇ .
  • the thermoplastic resin is a single resin selected from polyvinyl chloride resin, polypropylene resin, polyethylene terephthalate (PET) resin, polystyrene resin, ABS resin, polyphenylene ether resin, and polycarbonate (PC) resin.
  • PET polyethylene terephthalate
  • PC polycarbonate
  • the thermoplastic resin is a single resin selected from polystyrene resins, ABS resins, or a plurality of resin compositions.
  • polystyrene resin it is a resin which has as a main component a structure derived from styrene, and polystyrene and high impact polystyrene can be exemplified.
  • High impact polystyrene is polystyrene that includes HIPS and is reinforced with a rubber component.
  • the ABS resin refers to a resin containing, as a main component, a copolymer composed mainly of three components of acrylonitrile, butadiene and styrene.
  • Examples of carbon black include ketjen black, oil furnace black, acetylene black, furnace black, thermal black and channel black.
  • the average particle diameter of these is preferably 20 to 70 nm in terms of dispersibility and the like. If the addition amount is less than 5 parts by mass, sufficient conductivity can not be obtained, and the surface resistivity is too high. If it exceeds 60 parts by mass, the uniform dispersion with the resin is deteriorated, the molding processability is significantly reduced, and the mechanical strength Etc. will be reduced. Also, if the surface specific resistance exceeds 10 10 ⁇ , a sufficient antistatic effect can not be obtained, and if it is less than 10 2 ⁇ , the flow of electricity due to static electricity from the outside becomes easy and the electronic parts may be destroyed. is there.
  • These carbon blacks may contain up to 30 parts by mass of single layer or multilayer carbon nanofibers with respect to 100 parts by mass of carbon black in order to improve the conductivity within these ranges. It is not economically preferable that the single layer or multilayer carbon nanofibers are more than 30 parts by mass.
  • the cross copolymer is used in an amount of 10 to 100 parts by mass, preferably 15 to 60 parts by mass with respect to 100 parts by mass of the thermoplastic resin.
  • the cross copolymer is obtained by a manufacturing method comprising a polymerization step consisting of a coordination polymerization step and an anion polymerization step following this, and a single site coordination polymerization catalyst is used as the coordination polymerization step to obtain an ethylene unit amount.
  • Copolymer an aromatic vinyl compound monomer and an aromatic polyene monomer to synthesize an ethylene-aromatic vinyl compound-aromatic polyene copolymer chain, and then, as an anionic polymerization step, It is preferably a cross copolymer obtained by polymerization using an anionic polymerization initiator in the coexistence of an aromatic vinyl compound-aromatic polyene copolymer chain and an aromatic vinyl compound monomer, more preferably Further, the copolymer satisfies all the following conditions (1) to (3).
  • the content of the aromatic vinyl compound monomer unit of the ethylene-aromatic vinyl compound-aromatic polyene copolymer chain obtained in the coordination polymerization step is 5% by mole to 30% by mole, the amount of the aromatic polyene unit The content of the body unit is 0.01 mol% or more and 0.2 mol% or less, and the balance is the content of the ethylene monomer unit.
  • Weight-average molecular weight of the ethylene-aromatic vinyl compound-aromatic polyene copolymer chain obtained in the coordination polymerization step is 30,000 to 300,000, and molecular weight distribution (Mw / Mn) is 1.8 to 6 It is.
  • the content of the ethylene-aromatic vinyl compound-aromatic polyene copolymer chain contained in the cross copolymer is in the range of 50% by mass to 95% by mass.
  • the cross copolymer is preferably a copolymer having an ethylene-aromatic vinyl compound-aromatic polyene copolymer chain and an aromatic vinyl compound polymer chain, and an ethylene-aromatic vinyl compound-aromatic polyene copolymer.
  • Content of aromatic vinyl compound monomer unit of ethylene-aromatic vinyl compound-aromatic polyene copolymer chain is 5 mol% or more and 30 mol% or less, content of aromatic polyene monomer unit 0.01 It is the content of ethylene monomer units, with the remainder being mole% or more and 0.2 mol% or less.
  • the weight average molecular weight of the ethylene-aromatic vinyl compound-aromatic polyene copolymer chain is 50,000 or more and 300,000 or less, and the molecular weight distribution (Mw / Mn) is 1.8 or more and 6 or less.
  • the content of the ethylene-aromatic vinyl compound-aromatic polyene copolymer chain contained in the cross copolymer is in the range of 50% by mass to 95% by mass.
  • the cross copolymer is a copolymer having an ethylene-aromatic vinyl compound-aromatic polyene copolymer chain and an aromatic vinyl compound polymer chain, and an ethylene-aromatic vinyl compound-aromatic polyene copolymer
  • Content of aromatic vinyl compound monomer unit of ethylene-aromatic vinyl compound-aromatic polyene copolymer chain is 5 mol% or more and 30 mol% or less, content of aromatic polyene monomer unit 0.01 It is the content of ethylene monomer units, with the remainder being mole% or more and 0.2 mol% or less.
  • the weight average molecular weight of the ethylene-aromatic vinyl compound-aromatic polyene copolymer chain is 50,000 or more and 300,000 or less, and the molecular weight distribution (Mw / Mn) is 1.8 or more and 6 or less.
  • the content of the ethylene-aromatic vinyl compound-aromatic polyene copolymer chain contained in the cross copolymer is in the range of 50% by mass to 95% by mass.
  • the cross copolymer is a graft-through copolymer of an ethylene-aromatic vinyl compound-aromatic polyene copolymer chain and an aromatic vinyl compound polymer chain, and an ethylene-aromatic vinyl compound-aromatic polyene copolymer It is a cross copolymer in which a polymer chain and an aromatic vinyl compound polymer chain are linked via an aromatic polyene monomer unit, and all the following conditions (1) to (3) are satisfied Is preferred.
  • Content of aromatic vinyl compound monomer unit of ethylene-aromatic vinyl compound-aromatic polyene copolymer chain is 5 mol% or more and 30 mol% or less, content of aromatic polyene monomer unit 0.01 It is the content of ethylene units, with the remainder being from mol% to 0.2 mol%.
  • the weight average molecular weight of the ethylene-aromatic vinyl compound-aromatic polyene copolymer chain is 50,000 or more and 300,000 or less, and the molecular weight distribution (Mw / Mn) is 1.8 or more and 6 or less.
  • the content of the ethylene-aromatic vinyl compound-aromatic polyene copolymer chain contained in the cross copolymer is in the range of 50% by mass to 95% by mass.
  • the present cross copolymer is a copolymer having an ethylene-aromatic vinyl compound-aromatic polyene copolymer chain derived from a macromonomer and an aromatic vinyl compound polymer chain, and an ethylene-aromatic vinyl compound-aromatic compound It is characterized by having a structure in which the polyene copolymer chain and the aromatic vinyl compound polymer chain are linked via an aromatic polyene monomer unit.
  • the fact that the ethylene-aromatic vinyl compound-aromatic polyene copolymer chain and the aromatic vinyl compound polymer chain are linked via an aromatic polyene monomer unit can be proved by the following observable phenomenon.
  • the peak intensity (area) of the vinyl hydrogen (proton) of the divinylbenzene unit of the cross copolymer is compared with the peak intensity (area) of the divinylbenzene unit of the ethylene-styrene-divinylbenzene copolymer macromonomer. Less than 50%, preferably less than 20%.
  • divinylbenzene is also copolymerized simultaneously with the polymerization of styrene, and the ethylene-styrene-divinylbenzene copolymer chain and the polystyrene chain are linked via the divinylbenzene unit, so the anionic polymerization is performed.
  • the peak intensity of hydrogen (proton) of the vinyl group of the divinylbenzene unit is greatly reduced.
  • the peak of hydrogen (proton) of the vinyl group of the divinylbenzene unit is substantially eliminated in the cross copolymer after anionic polymerization. Details are described in the well-known literature "Synthesis of branched copolymer using olefin copolymer containing divinylbenzene unit", Arai Akira, Hasegawa Masaru, Japan Rubber Association Journal, p 382, vol. 82 (2009).
  • the ethylene-aromatic vinyl compound-aromatic polyene copolymer chain and the aromatic vinyl compound polymer chain are linked via an aromatic polyene monomer unit (one example)
  • aromatic polyene monomer unit one example
  • the fact that the ethylene-styrene-divinylbenzene copolymer chain and the polystyrene chain are linked via a divinylbenzene unit) can be proved by the following observable phenomenon. That is, even after Soxhlet extraction is performed a sufficient number of times with the present cross copolymer using an appropriate solvent, the contained ethylene-styrene-divinylbenzene copolymer chain and polystyrene chain can not be separated.
  • ethylene-styrene-divinylbenzene copolymer having the same composition as the ethylene-styrene-divinylbenzene copolymer chain contained in the present cross copolymer and polystyrene are subjected to Soxhlet extraction with boiling acetone to obtain an acetone insoluble portion
  • ethylene-styrene-divinylbenzene copolymer it can be fractionated into polystyrene as an acetone soluble part.
  • the cross copolymer has ethylene-aromatic vinyl compound-aromatic polyene copolymer chain and aromatic vinyl compound polymer chain, and ethylene-
  • the copolymer is preferably a copolymer having a structure in which an aromatic vinyl compound-aromatic polyene copolymer chain and an aromatic vinyl compound polymer chain are linked via an aromatic polyene monomer unit.
  • the present cross copolymer may contain a relatively small amount of an aromatic vinyl compound (polystyrene) homopolymer. More preferably, they are copolymers satisfying all the following conditions (1) to (3).
  • the content of the aromatic vinyl monomer unit of the ethylene-aromatic vinyl compound-aromatic polyene copolymer chain obtained in the coordination polymerization step is 5 mol% or more and 30 mol% or less, preferably 10 mol% or more The content is 30 mol% or less, the content of aromatic polyene monomer units is 0.01 mol% or more and 0.2 mol% or less, and the balance is the content of ethylene units.
  • the weight average molecular weight of the ethylene-aromatic vinyl compound-aromatic polyene copolymer chain obtained in the coordination polymerization step is 50,000 to 300,000, and the molecular weight distribution (Mw / Mn) is 1.8 to 6 It is.
  • the content of the ethylene-aromatic vinyl compound-aromatic polyene copolymer chain contained in the cross copolymer is in the range of 50% by mass to 95% by mass.
  • the present cross copolymer will be described from another viewpoint.
  • the present cross copolymer is obtained by a manufacturing method including a polymerization step consisting of a coordination polymerization step and an anion polymerization step, and a single site coordination polymerization catalyst is used as the coordination polymerization step, and a single amount of ethylene or aromatic vinyl compound is used.
  • the ethylene-aromatic vinyl compound-aromatic polyene copolymer chain is synthesized by copolymerizing a monomer and an aromatic polyene monomer, and then this ethylene-aromatic vinyl compound-aromatic polyene is synthesized as an anionic polymerization step.
  • it is a copolymer manufactured by anion polymerization by an anion polymerization initiator in the coexistence of a copolymer chain and an aromatic vinyl compound monomer.
  • aromatic vinyl compound monomer used in the anionic polymerization step either an unreacted monomer remaining in the polymerization solution in the coordination polymerization step or an aromatic vinyl compound monomer may be newly added to this good.
  • An anionic polymerization is initiated by the addition of an anionic polymerization initiator to the polymerization solution, but in this case, the aromatic polyene monomer unit of the ethylene-aromatic vinyl compound-aromatic polyene copolymer chain is added to the polymerization solution and In comparison, an anionic polymerization substantially starts from an aromatic vinyl compound monomer contained in an overwhelmingly large amount, and an ethylene-aromatic vinyl compound-aromatic polyene copolymer is obtained while the aromatic vinyl monomer is polymerized. The polymerization proceeds while the vinyl group of the aromatic polyene monomer unit of the chain is also copolymerized.
  • the cross copolymer obtained is known to those skilled in the art and known in the art, the ethylene-aromatic vinyl compound-aromatic polyene copolymer chain as the main chain and the aromatic vinyl compound polymer chain as the cross chain It is considered that a large number of structures (cross bonds) bonded in a graft-through manner are included.
  • the expression for defining the cross copolymer is preferably a graft-through copolymer of an ethylene-aromatic vinyl compound-aromatic polyene copolymer chain and an aromatic vinyl compound polymer chain.
  • aromatic vinyl compound monomer styrene and various substituted styrenes such as p-methylstyrene, m-methylstyrene, o-methylstyrene, o-t-butylstyrene, m-t-butylstyrene, pt And monomers derived from each styrenic monomer such as -butylstyrene, p-chlorostyrene, o-chlorostyrene and the like.
  • styrene, p-methylstyrene, p-chlorostyrene, particularly preferably styrene are used.
  • These aromatic vinyl compound monomers may be used alone or in combination of two or more.
  • the aromatic polyene monomer has a carbon number of 10 or more and 30 or less, has a plurality of double bonds (vinyl group) and one or more aromatic groups, and one of the double bonds (vinyl group) is Even when used in coordination polymerization, the remaining double bonds are anionically polymerizable aromatic polyenes.
  • any one or a mixture of two or more of ortho divinylbenzene, paradivinylbenzene and metadivinylbenzene is suitably used.
  • a polyethylene resin may be further added to the conductive resin composition of the present invention.
  • the addition amount thereof is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the thermoplastic resin.
  • the polyethylene-based resin is not particularly limited, but ethylene-methacrylic acid ester copolymer, ethylene-acrylic acid ester copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, low density polyethylene resin ( It is preferable to use a polyethylene resin represented by LDPE), high density polyethylene resin (HDPE), and linear low density polyethylene resin (LLDPE).
  • the melt flow index of the polyethylene resin is preferably 0.1 g / 10 min or more at 190 ° C. and a load of 2.16 kg (measured in accordance with JIS-K-7210).
  • the addition of the polyethylene-based resin makes it possible to further reduce the desorption of carbon black. If the addition amount is less than 1 part by mass, the effect is insufficient, and if it exceeds 30 parts by mass, it may be difficult to uniformly disperse in the polystyrene resin and the ABS resin, and the effect may not be exhibited.
  • the conductive resin composition of the present invention when filled with carbon black so as to have a surface specific resistance value of 10 2 to 10 10 ⁇ , in order to maintain sufficient moldability, melt flow index (JIS- Measured according to K-7210) at a temperature of 200 ° C. under a load of 5 kg in the case of polystyrene-based resin, and at a temperature of 220 ° C. under a load of 10 kg under 0.1 g / 10 min. Is preferred.
  • the present conductive resin composition has a tensile modulus of elasticity, a breaking point strength and a bending resistance suitable as an electronic component packaging container.
  • the tensile modulus is about 1000 MPa or more and 3000 MPa or less
  • the breaking point strength is 25 MPa or more and 50 MPa or less
  • the bending resistance is 100 times or more, preferably 300 times or more.
  • the conductive resin composition of the present invention is usually a resin, such as a lubricant, a plasticizer, a processing aid, a reinforcing agent, a stabilizer, etc., in order to improve the flow characteristics of the composition and the mechanical properties of the molded article, if necessary. It is possible to add various additives and other resin components used in
  • knead and pelletize the raw materials to obtain a resin composition known methods such as a Banbury mixer and an extruder can be used.
  • the order of kneading is arbitrary, and it is also possible to knead the raw materials together at the time of kneading, or, for example, a mixture of a cross copolymer and carbon black, and a mixture of a thermoplastic resin and a cross copolymer separately. It is also possible to knead in stages, such as kneading and finally knead
  • the conductive resin composition of the present invention exhibits good mechanical properties and moldability, and can be suitably used as an electronic component packaging container in that the detachment of carbon black due to contact or friction is very small.
  • the conductive resin composition can be molded by any known method and suitably used as an electronic component packaging container.
  • the electronic component packaging container is a packaging container for electronic components, for example, a tray, a magazine tube, a carrier tape (in a known method such as injection molding, vacuum forming, pressure forming, hot plate forming etc.) It can be used as an electronic component packaging container such as embossed carrier tape). In particular, it is suitably used for carrier tapes and trays.
  • An electronic component package is obtained by housing the electronic component in the electronic component packaging container. In this case, the container is capped if necessary. For example, in the case of a carrier tape, a lid with a cover tape is provided after housing the electronic component. An electronic component package includes such a thing.
  • the sheet of the conductive resin composition may be a single layer sheet or a multilayer sheet.
  • a multilayer sheet is one having a layer of a conductive resin composition on at least one side of a substrate layer made of a thermoplastic resin.
  • the thermoplastic resin of the base material layer is not particularly limited, but for example, polystyrene resin, ABS resin, polycarbonate resin and the like can be used, preferably one or more selected from polystyrene resin and ABS resin is used .
  • the thermoplastic resin of the base material layer is preferably the same resin as the thermoplastic resin used for the conductive resin composition of the present invention, from the viewpoint of the adhesiveness between the layers.
  • the thickness of the sheet is preferably 0.1 to 3.0 mm, and in the case of a multilayer sheet, the thickness of the layer of the conductive resin composition in the entire thickness may be 2% to 80%.
  • the electronic component is not particularly limited, and, for example, an IC, a resistor, a capacitor, an inductor, a transistor, a diode, an LED (light emitting diode), a liquid crystal, a piezoelectric element resistor, a filter, a quartz oscillator, a quartz oscillator, a connector, a switch, a volume , Relay etc.
  • IC integrated circuit
  • resistor resistor
  • a capacitor an inductor
  • a transistor a diode
  • an LED light emitting diode
  • quartz oscillator a quartz oscillator
  • a connector a switch
  • a switch a volume , Relay etc.
  • the raw material resin used for the Example and the comparative example and the manufacturing method are as follows.
  • the evaluation was performed by the following method.
  • thermoplastic resin used is as follows. Polystyrene: Toyo Styrene HRM-12 Impact-resistant polystyrene resin (HIPS): Toyo Styrene Co. HI-E4 ABS: Denka Co., Ltd. Denka ABS SE-10
  • Carbon black used is Denka Black granular product manufactured by Denka Co., Ltd.
  • Cross copolymer> The following cross copolymers 1 to 3 were used. These cross copolymers are produced by the production methods of Examples or Comparative Examples described in WO 2000/37517, WO 2007/139116, and JP 2009-120792 A, and the following compositions are similarly described in these publications. It asked by the method of.
  • the styrene content, divinylbenzene content, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), cross copolymer of ethylene-styrene-divinylbenzene copolymer used to define the cross copolymer The content of ethylene-styrene-divinylbenzene copolymer, the weight average molecular weight (Mw) of polystyrene chains, and the molecular weight distribution (Mw / Mn) are shown.
  • EEA ethylene-ethyl acrylate resin
  • DPDJ-6169 manufactured by Nippon Unicar Co., Ltd.
  • HDPE high density polyethylene resin
  • HYZEX 5000H manufactured by Prime Polymer Co.
  • SEBS hydrogenated styrene-butadiene copolymer resin
  • the conductive resin composition of the present invention exhibits very good carbon releasability (low carbon while showing good mechanical properties (tensile elastic modulus, breaking strength, bending resistance) and surface resistance values in an appropriate range. Releasability). Therefore, it is suitable as a material for electronic component packaging containers.

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  • Chemical Kinetics & Catalysis (AREA)
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Abstract

[Problem] The purpose of the present invention is to provide an electroconductive sheet in which contamination of an IC or the like caused by the shedding of carbon black or the like due to wear caused by contact with the IC or the like is dramatically reduced, as well as an electronic component packaging container or electronic component package obtained by molding said sheet. [Solution] An electroconductive resin composition containing 5–60 parts by mass carbon black and 10–100 parts by mass cross-copolymer per 100 parts by mass thermoplastic resin, and having a surface specific resistance of 102–1010Ω, as well as an electronic component packaging container or electronic component package using the same.

Description

導電性樹脂組成物Conductive resin composition
　本発明は導電性樹脂組成物に関し、該導電性樹脂組成物は例えば電子部品包装用に好適に用いる事ができる。 The present invention relates to a conductive resin composition, and the conductive resin composition can be suitably used, for example, for packaging electronic components.
　ＩＣ等の電子部品の包装容器にはインジェクショントレー、真空成形トレー、マガジン、エンボスキャリアテープ、カバーテープなどがある。これら電子部品の包装容器には電子部品と容器との摩擦により、あるいは容器から蓋材を剥離する際に発生する静電気により収納しているＩＣ等が破壊されることを防止するために導電性樹脂組成物が用いられる。導電性樹脂組成物としては熱可塑性樹脂と導電性フィラーからなるものが知られている。導電性フィラーとしては金属微粉末、カーボンファイバー、カーボンブラックなどがあるが、カーボンブラックが混練条件等の検討により均一に分散させることが可能であり、安定した表面固有抵抗値が得られ易いことから多く使用されている。熱可塑性樹脂としては、ポリ塩化ビニル系樹脂、ポリプロピレン系樹脂、ポリエチレンテレフタレート系樹脂、ポリスチレン系樹脂およびＡＢＳ系樹脂が、また１００℃以上での耐熱用としてポリフェニレンエーテル系樹脂、ポリカーボネート樹脂などが用いられている。これらの樹脂のなかで耐熱用においてはポリフェニレンエーテル系樹脂が、一般用としてはポリスチレン系樹脂およびＡＢＳ系樹脂が、他の樹脂に比べカーボンブラックを多量に添加しても流動性や成形性の著しい低下がなく、さらにコストの面でも優れている。 Packaging containers for electronic parts such as ICs include injection trays, vacuum formed trays, magazines, embossed carrier tapes, cover tapes and the like. In order to prevent the IC etc. stored in the packaging container of these electronic parts from being destroyed by the friction between the electronic parts and the container or by the static electricity generated when peeling the lid material from the container, the conductive resin The composition is used. As a conductive resin composition, what consists of a thermoplastic resin and a conductive filler is known. There are fine metal powder, carbon fiber, carbon black etc. as the conductive filler, but it is possible to disperse carbon black uniformly by examination of kneading conditions etc. and it is easy to obtain stable surface specific resistance value Many are used. As the thermoplastic resin, polyvinyl chloride resin, polypropylene resin, polyethylene terephthalate resin, polystyrene resin and ABS resin are used, and for heat resistance at 100 ° C. or higher, polyphenylene ether resin, polycarbonate resin, etc. are used. ing. Among these resins, polyphenylene ether-based resins for heat resistance, polystyrene-based resins and ABS-based resins for general use, and even if a large amount of carbon black is added compared to other resins, the fluidity and the formability are remarkable There is no decline and the cost is excellent.
　しかしながらカーボンブラックを多量に添加した組成物の成形品は、摩耗により成形品の表面から、カーボンブラックが脱離し易いという欠点がある。従来、ＳＥＢＳ等のエラストマー成分を添加して本課題に対応してきたが十分とはいえない状況であった（特許文献１～３）。本発明は、かかる欠点を解決するものであり、ポリスチレン系樹脂及びＡＢＳ系樹脂から選ばれた少なくとも１種類の熱可塑性樹脂およびカーボンブラックからなる導電性樹脂組成物において、この導電性樹脂組成物にクロス共重合体を含有させることにより、樹脂としての力学物性を維持しつつＩＣ等との接触時の摩耗によるカーボンブラック等の脱離が原因となるＩＣ等の汚染を著しく減少させた導電性樹脂組成物を提供しようとするものである。 However, a molded article of a composition to which a large amount of carbon black is added has a disadvantage that carbon black is easily detached from the surface of the molded article due to abrasion. Heretofore, this problem has been addressed by adding an elastomer component such as SEBS, but the situation is not sufficient (Patent Documents 1 to 3). The present invention solves the above-mentioned drawbacks, and a conductive resin composition comprising at least one thermoplastic resin selected from polystyrene resins and ABS resins and carbon black, the conductive resin composition comprising A conductive resin in which contamination of IC and the like caused by detachment of carbon black and the like due to abrasion at the time of contact with an IC and the like is remarkably reduced while maintaining mechanical properties as a resin by containing a cross copolymer. It is an object of the present invention to provide a composition.
特開平９－７６４２５号JP-A-9-76425 特開２００３－７３５４１号JP 2003-73541 特開２００２－３５５９３５号Japanese Patent Application Laid-Open No. 2002-355935
　ＩＣ等との接触時の摩耗によるカーボンブラック等の脱離が原因となるＩＣ等の汚染を著しく減少させた導電性樹脂組成物およびシート、並びに当該シートを成形してなる電子部品包装容器や電子部品包装体を提供することを目的とするものである。 Conductive resin composition and sheet having significantly reduced contamination of IC and the like caused by detachment of carbon black and the like due to abrasion at the time of contact with IC and the like, and electronic component packaging container and electronic formed by molding the sheet It aims at providing a parts package.
　以上の課題を解決する手段は以下の通りである。
〔１〕熱可塑性樹脂１００質量部に対し、カーボンブラック５～６０質量部、クロス共重合体１０～１００質量部を含有し、その表面固有抵抗値が１０２～１０１０Ωである導電性樹脂組成物。
〔２〕前記熱可塑性樹脂が、ポリスチレン系樹脂及びＡＢＳ樹脂から選ばれる一種以上である、〔１〕記載の導電性樹脂組成物。
〔３〕前記クロス共重合体が、エチレン－芳香族ビニル化合物－芳香族ポリエン共重合体鎖と芳香族ビニル化合物重合体鎖を有する共重合体であり、エチレン－芳香族ビニル化合物－芳香族ポリエン共重合体鎖と芳香族ビニル化合物重合体鎖が芳香族ポリエン単量体単位を介して結合する構造を有しており、かつ以下の（１）～（３）の条件を満足する共重合体である、〔１〕または〔２〕に記載の導電性樹脂組成物。
（１）エチレン－芳香族ビニル化合物－芳香族ポリエン共重合体鎖の芳香族ビニル化合物単量体単位の含量が５モル％以上３０モル％以下、芳香族ポリエン単量体単位の含量が０．０１モル％以上０．２モル％以下、残部がエチレン単量体単位の含量である。
（２）エチレン－芳香族ビニル化合物－芳香族ポリエン共重合体鎖の重量平均分子量が５万以上３０万以下、分子量分布（Ｍｗ／Ｍｎ）が１．８以上６以下である。
（３）クロス共重合体中に含まれるエチレン－芳香族ビニル化合物－芳香族ポリエン共重合体鎖の含量が５０質量％以上９５質量％以下の範囲にある。
〔４〕さらにポリエチレン系樹脂を、前記熱可塑性樹脂１００質量部に対し１～３０質量部含む、〔１〕～〔３〕のいずれか一項に記載の導電性樹脂組成物。
〔５〕〔１〕～〔４〕のいずれか一項に記載の導電性樹脂組成物を用いた電子部品包装容器。
〔６〕〔１〕～〔４〕のいずれか一項に記載の導電性樹脂組成物を用いた電子部品包装体。
〔７〕〔１〕～〔４〕のいずれか一項に記載の導電性樹脂組成物を用いたシート。
〔８〕ポリスチレン系樹脂及びＡＢＳ系樹脂から選ばれた少なくとも１種類の熱可塑性樹脂からなる基材層の、少なくとも片面に〔１〕～〔４〕のいずれか一項記載の導電性樹脂組成物を積層した多層シート。
〔９〕〔７〕又は〔８〕に記載のシートを用いた電子部品包装容器。
〔１０〕〔７〕又は〔８〕に記載のシートを用いた電子部品包装体。 The means for solving the above problems are as follows.
[1] A conductive resin containing 5 to 60 parts by mass of carbon black and 10 to 100 parts by mass of a cross copolymer with respect to 100 parts by mass of a thermoplastic resin and having a surface resistivity of 10 2 to 10 10 Ω. Composition.
[2] The conductive resin composition according to [1], wherein the thermoplastic resin is one or more selected from a polystyrene resin and an ABS resin.
[3] The cross copolymer is a copolymer having an ethylene-aromatic vinyl compound-aromatic polyene copolymer chain and an aromatic vinyl compound polymer chain, and is an ethylene-aromatic vinyl compound-aromatic polyene A copolymer having a structure in which a copolymer chain and an aromatic vinyl compound polymer chain are linked via an aromatic polyene monomer unit, and satisfying the following conditions (1) to (3): The conductive resin composition according to [1] or [2], which is
(1) The content of the aromatic vinyl compound monomer unit of the ethylene-aromatic vinyl compound-aromatic polyene copolymer chain is 5 mol% or more and 30 mol% or less, and the content of the aromatic polyene monomer unit is 0. 01 mol% or more and 0.2 mol% or less, the balance is the content of ethylene monomer units.
(2) The weight average molecular weight of the ethylene-aromatic vinyl compound-aromatic polyene copolymer chain is 50,000 or more and 300,000 or less, and the molecular weight distribution (Mw / Mn) is 1.8 or more and 6 or less.
(3) The content of the ethylene-aromatic vinyl compound-aromatic polyene copolymer chain contained in the cross copolymer is in the range of 50% by mass to 95% by mass.
[4] The conductive resin composition according to any one of [1] to [3], further comprising 1 to 30 parts by mass of a polyethylene-based resin with respect to 100 parts by mass of the thermoplastic resin.
[5] An electronic component packaging container using the conductive resin composition according to any one of [1] to [4].
[6] An electronic component package using the conductive resin composition according to any one of [1] to [4].
[7] A sheet using the conductive resin composition according to any one of [1] to [4].
[8] The conductive resin composition according to any one of [1] to [4] on at least one side of a base material layer comprising at least one thermoplastic resin selected from polystyrene resins and ABS resins. Multi-layered sheet laminated.
The electronic component packaging container using the sheet as described in [9] [7] or [8].
The electronic component package which used the sheet as described in [10] [7] or [8].
　本発明の導電性樹脂組成物は、良好な力学物性や成形加工性を示し、さらに、接触や摩擦によるカーボンブラックの脱離が非常に少ないという点で、たとえばシートとして電子部品包装容器として好適に使用できる。 The conductive resin composition of the present invention exhibits favorable mechanical properties and molding processability, and further, is very suitable as an electronic component packaging container as a sheet, for example, in that there is very little detachment of carbon black due to contact or friction. It can be used.
　以下、本発明の導電性樹脂組成物を詳細に説明する。 Hereinafter, the conductive resin composition of the present invention will be described in detail.
　本発明は熱可塑性樹脂１００質量部に対し、カーボンブラック５～６０質量部、クロス共重合体１０～１００質量部を含有し、その表面固有抵抗値が１０２～１０１０Ωである導電性樹脂組成物である。ここで、熱可塑性樹脂は、ポリ塩化ビニル系樹脂、ポリプロピレン系樹脂、ポリエチレンテレフタレート（ＰＥＴ）系樹脂、ポリスチレン系樹脂、ＡＢＳ系樹脂、ポリフェニレンエーテル系樹脂、ポリカーボネート（ＰＣ）樹脂から選ばれる単数の樹脂、または複数の樹脂組成物が好ましく、特に好ましくは前記熱可塑性樹脂が、ポリスチレン系樹脂、ＡＢＳ樹脂から選ばれる単数の樹脂、または複数の樹脂組成物である。ここでポリスチレン系樹脂としては、スチレンから誘導される構造を主成分とする樹脂で、ポリスチレン、耐衝撃性ポリスチレンが例示できる。耐衝撃性ポリスチレンとはＨＩＰＳを包含し、ゴム成分により補強されたポリスチレンである。また、ＡＢＳ系樹脂とはアクリルニトリル、ブタジエン、スチレンの三成分を主体とした共重合体を主成分とするものをいう。 The present invention is a conductive resin containing 5 to 60 parts by mass of carbon black and 10 to 100 parts by mass of a cross copolymer with respect to 100 parts by mass of a thermoplastic resin and having a surface resistivity of 10 2 to 10 10 Ω. It is a composition. Here, the thermoplastic resin is a single resin selected from polyvinyl chloride resin, polypropylene resin, polyethylene terephthalate (PET) resin, polystyrene resin, ABS resin, polyphenylene ether resin, and polycarbonate (PC) resin. Or a plurality of resin compositions are preferable, and particularly preferably, the thermoplastic resin is a single resin selected from polystyrene resins, ABS resins, or a plurality of resin compositions. Here, as a polystyrene resin, it is a resin which has as a main component a structure derived from styrene, and polystyrene and high impact polystyrene can be exemplified. High impact polystyrene is polystyrene that includes HIPS and is reinforced with a rubber component. In addition, the ABS resin refers to a resin containing, as a main component, a copolymer composed mainly of three components of acrylonitrile, butadiene and styrene.
　カーボンブラックは、例えば、ケッチェンブラック、オイルファーネスブラック、アセチレンブラック、ファーネスブラック、サーマルブラック、チャネルブラックが挙げられる。これらの平均粒径は分散性等の点から、２０～７０ｎｍが好ましい。添加量が５質量部未満では十分な導電性が得られず表面固有抵抗値が高くなりすぎ、６０質量部を越えると樹脂との均一分散性の悪化、成形加工性の著しい低下、機械的強度等の特性値が低下してしまう。また、表面固有抵抗値が１０１０Ωを越えると十分な帯電防止効果が得られず、１０２Ω未満では外部から静電気等による電気の流入を容易にし、電子部品が破壊してしまう可能性がある。これらカ－ボンブラックは、これらの範囲内での導電率向上のため、カーボンブラック１００質量部に対し、最大３０質量部までの単層または多層のカーボンナノファイバーを含んでも良い。単層または多層のカーボンナノファイバーが３０質量部より多いと経済的に好ましくない。 Examples of carbon black include ketjen black, oil furnace black, acetylene black, furnace black, thermal black and channel black. The average particle diameter of these is preferably 20 to 70 nm in terms of dispersibility and the like. If the addition amount is less than 5 parts by mass, sufficient conductivity can not be obtained, and the surface resistivity is too high. If it exceeds 60 parts by mass, the uniform dispersion with the resin is deteriorated, the molding processability is significantly reduced, and the mechanical strength Etc. will be reduced. Also, if the surface specific resistance exceeds 10 10 Ω, a sufficient antistatic effect can not be obtained, and if it is less than 10 2 Ω, the flow of electricity due to static electricity from the outside becomes easy and the electronic parts may be destroyed. is there. These carbon blacks may contain up to 30 parts by mass of single layer or multilayer carbon nanofibers with respect to 100 parts by mass of carbon black in order to improve the conductivity within these ranges. It is not economically preferable that the single layer or multilayer carbon nanofibers are more than 30 parts by mass.
　クロス共重合体は、前記熱可塑性樹脂１００質量部に対し、１０～１００質量部、好ましくは１５質量部～６０質量部を用いる。ここでクロス共重合体とは、配位重合工程とこれに続くアニオン重合工程からなる重合工程からなる製造方法により得られ、配位重合工程として、シングルサイト配位重合触媒を用いてエチレン単量体、芳香族ビニル化合物単量体及び芳香族ポリエン単量体の共重合を行い、エチレン－芳香族ビニル化合物－芳香族ポリエン共重合体鎖を合成し、次にアニオン重合工程として、このエチレン－芳香族ビニル化合物－芳香族ポリエン共重合体鎖と芳香族ビニル化合物単量体の共存下、アニオン重合開始剤を用いて重合することで得られるクロス共重合体であることが好ましく、より好ましくは、さらに以下の（１）～（３）の条件をすべて満足する共重合体である。
（１）配位重合工程で得られるエチレン－芳香族ビニル化合物－芳香族ポリエン共重合体鎖の芳香族ビニル化合物単量体単位の含量が５モル％以上３０モル％以下、芳香族ポリエン単量体単位の含量０．０１モル％以上０．２モル％以下、残部がエチレン単量体単位の含量である。
（２）配位重合工程で得られるエチレン－芳香族ビニル化合物－芳香族ポリエン共重合体鎖の重量平均分子量が３万以上３０万以下、分子量分布（Ｍｗ／Ｍｎ）が１．８以上６以下である。
（３）クロス共重合体中に含まれるエチレン－芳香族ビニル化合物－芳香族ポリエン共重合体鎖の含量が５０質量％以上９５質量％以下の範囲にある。 The cross copolymer is used in an amount of 10 to 100 parts by mass, preferably 15 to 60 parts by mass with respect to 100 parts by mass of the thermoplastic resin. Here, the cross copolymer is obtained by a manufacturing method comprising a polymerization step consisting of a coordination polymerization step and an anion polymerization step following this, and a single site coordination polymerization catalyst is used as the coordination polymerization step to obtain an ethylene unit amount. Copolymer, an aromatic vinyl compound monomer and an aromatic polyene monomer to synthesize an ethylene-aromatic vinyl compound-aromatic polyene copolymer chain, and then, as an anionic polymerization step, It is preferably a cross copolymer obtained by polymerization using an anionic polymerization initiator in the coexistence of an aromatic vinyl compound-aromatic polyene copolymer chain and an aromatic vinyl compound monomer, more preferably Further, the copolymer satisfies all the following conditions (1) to (3).
(1) The content of the aromatic vinyl compound monomer unit of the ethylene-aromatic vinyl compound-aromatic polyene copolymer chain obtained in the coordination polymerization step is 5% by mole to 30% by mole, the amount of the aromatic polyene unit The content of the body unit is 0.01 mol% or more and 0.2 mol% or less, and the balance is the content of the ethylene monomer unit.
(2) Weight-average molecular weight of the ethylene-aromatic vinyl compound-aromatic polyene copolymer chain obtained in the coordination polymerization step is 30,000 to 300,000, and molecular weight distribution (Mw / Mn) is 1.8 to 6 It is.
(3) The content of the ethylene-aromatic vinyl compound-aromatic polyene copolymer chain contained in the cross copolymer is in the range of 50% by mass to 95% by mass.
　クロス共重合体は、好ましくはエチレン－芳香族ビニル化合物－芳香族ポリエン共重合体鎖と芳香族ビニル化合物重合体鎖を有する共重合体であり、エチレン－芳香族ビニル化合物－芳香族ポリエン共重合体鎖と芳香族ビニル化合物重合体鎖が芳香族ポリエン単量体単位を介して結合する構造を有しており、かつ以下の（１）～（３）の条件を満足する共重合体である。
（１）エチレン－芳香族ビニル化合物－芳香族ポリエン共重合体鎖の芳香族ビニル化合物単量体単位の含量が５モル％以上３０モル％以下、芳香族ポリエン単量体単位の含量０．０１モル％以上０．２モル％以下、残部がエチレン単量体単位の含量である。
（２）エチレン－芳香族ビニル化合物－芳香族ポリエン共重合体鎖の重量平均分子量が５万以上３０万以下、分子量分布（Ｍｗ／Ｍｎ）が１．８以上６以下である。
（３）クロス共重合体中に含まれるエチレン－芳香族ビニル化合物－芳香族ポリエン共重合体鎖の含量が５０質量％以上９５質量％以下の範囲にある。 The cross copolymer is preferably a copolymer having an ethylene-aromatic vinyl compound-aromatic polyene copolymer chain and an aromatic vinyl compound polymer chain, and an ethylene-aromatic vinyl compound-aromatic polyene copolymer. A copolymer having a structure in which a combined chain and an aromatic vinyl compound polymer chain are linked via an aromatic polyene monomer unit, and satisfying the following conditions (1) to (3): .
(1) Content of aromatic vinyl compound monomer unit of ethylene-aromatic vinyl compound-aromatic polyene copolymer chain is 5 mol% or more and 30 mol% or less, content of aromatic polyene monomer unit 0.01 It is the content of ethylene monomer units, with the remainder being mole% or more and 0.2 mol% or less.
(2) The weight average molecular weight of the ethylene-aromatic vinyl compound-aromatic polyene copolymer chain is 50,000 or more and 300,000 or less, and the molecular weight distribution (Mw / Mn) is 1.8 or more and 6 or less.
(3) The content of the ethylene-aromatic vinyl compound-aromatic polyene copolymer chain contained in the cross copolymer is in the range of 50% by mass to 95% by mass.
　さらにクロス共重合体が、エチレン－芳香族ビニル化合物－芳香族ポリエン共重合体鎖と芳香族ビニル化合物重合体鎖を有する共重合体であり、エチレン－芳香族ビニル化合物－芳香族ポリエン共重合体鎖と芳香族ビニル化合物重合体鎖が芳香族ポリエン単量体単位を介して結合する構造を有しており、かつ以下の（１）～（３）の条件をすべて満足するクロス共重合体であることが好ましい。
（１）エチレン－芳香族ビニル化合物－芳香族ポリエン共重合体鎖の芳香族ビニル化合物単量体単位の含量が５モル％以上３０モル％以下、芳香族ポリエン単量体単位の含量０．０１モル％以上０．２モル％以下、残部がエチレン単量体単位の含量である。
（２）エチレン－芳香族ビニル化合物－芳香族ポリエン共重合体鎖の重量平均分子量が５万以上３０万以下、分子量分布（Ｍｗ／Ｍｎ）が１．８以上６以下である。
（３）クロス共重合体中に含まれるエチレン－芳香族ビニル化合物－芳香族ポリエン共重合体鎖の含量が５０質量％以上９５質量％以下の範囲にある。 Furthermore, the cross copolymer is a copolymer having an ethylene-aromatic vinyl compound-aromatic polyene copolymer chain and an aromatic vinyl compound polymer chain, and an ethylene-aromatic vinyl compound-aromatic polyene copolymer A cross copolymer having a structure in which a chain and an aromatic vinyl compound polymer chain are linked via an aromatic polyene monomer unit, and satisfying all the following conditions (1) to (3): Is preferred.
(1) Content of aromatic vinyl compound monomer unit of ethylene-aromatic vinyl compound-aromatic polyene copolymer chain is 5 mol% or more and 30 mol% or less, content of aromatic polyene monomer unit 0.01 It is the content of ethylene monomer units, with the remainder being mole% or more and 0.2 mol% or less.
(2) The weight average molecular weight of the ethylene-aromatic vinyl compound-aromatic polyene copolymer chain is 50,000 or more and 300,000 or less, and the molecular weight distribution (Mw / Mn) is 1.8 or more and 6 or less.
(3) The content of the ethylene-aromatic vinyl compound-aromatic polyene copolymer chain contained in the cross copolymer is in the range of 50% by mass to 95% by mass.
　さらに、クロス共重合体が、エチレン－芳香族ビニル化合物－芳香族ポリエン共重合体鎖と芳香族ビニル化合物重合体鎖のグラフトスルー共重合体であり、エチレン－芳香族ビニル化合物－芳香族ポリエン共重合体鎖と芳香族ビニル化合物重合体鎖が芳香族ポリエン単量体単位を介して結合しており、かつ以下の（１）～（３）の条件をすべて満足するクロス共重合体であることが好ましい。
（１）エチレン－芳香族ビニル化合物－芳香族ポリエン共重合体鎖の芳香族ビニル化合物単量体単位の含量が５モル％以上３０モル％以下、芳香族ポリエン単量体単位の含量０．０１モル％以上０．２モル％以下、残部がエチレン単位の含量である。
（２）エチレン－芳香族ビニル化合物－芳香族ポリエン共重合体鎖の重量平均分子量が５万以上３０万以下、分子量分布（Ｍｗ／Ｍｎ）が１．８以上６以下である。
（３）クロス共重合体中に含まれるエチレン－芳香族ビニル化合物－芳香族ポリエン共重合体鎖の含量が５０質量％以上９５質量％以下の範囲にある。 Further, the cross copolymer is a graft-through copolymer of an ethylene-aromatic vinyl compound-aromatic polyene copolymer chain and an aromatic vinyl compound polymer chain, and an ethylene-aromatic vinyl compound-aromatic polyene copolymer It is a cross copolymer in which a polymer chain and an aromatic vinyl compound polymer chain are linked via an aromatic polyene monomer unit, and all the following conditions (1) to (3) are satisfied Is preferred.
(1) Content of aromatic vinyl compound monomer unit of ethylene-aromatic vinyl compound-aromatic polyene copolymer chain is 5 mol% or more and 30 mol% or less, content of aromatic polyene monomer unit 0.01 It is the content of ethylene units, with the remainder being from mol% to 0.2 mol%.
(2) The weight average molecular weight of the ethylene-aromatic vinyl compound-aromatic polyene copolymer chain is 50,000 or more and 300,000 or less, and the molecular weight distribution (Mw / Mn) is 1.8 or more and 6 or less.
(3) The content of the ethylene-aromatic vinyl compound-aromatic polyene copolymer chain contained in the cross copolymer is in the range of 50% by mass to 95% by mass.
　以下、本発明に用いるクロス共重合体について説明する。本クロス共重合体は、マクロモノマーに由来するエチレン－芳香族ビニル化合物－芳香族ポリエン共重合体鎖と芳香族ビニル化合物重合体鎖を有する共重合体であり、エチレン－芳香族ビニル化合物－芳香族ポリエン共重合体鎖と芳香族ビニル化合物重合体鎖が芳香族ポリエン単量体単位を介して結合している構造を有することを特徴としている。エチレン－芳香族ビニル化合物－芳香族ポリエン共重合体鎖と芳香族ビニル化合物重合体鎖が芳香族ポリエン単量体単位を介して結合していることは、以下の観察可能な現象で証明できる。ここでは代表的なエチレン－スチレン－ジビニルベンゼン共重合体鎖とポリスチレン鎖がジビニルベンゼン単位を介して結合している例について示す。すなわち配位重合工程で得られたエチレン－スチレン－ジビニルベンゼン共重合体マクロモノマーと、本共重合体とスチレンの存在下でのアニオン重合を経て得られるクロス共重合体の１Ｈ－ＮＭＲ（プロトンＮＭＲ）を測定し、両者のジビニルベンゼン単位のビニル基水素（プロトン）のピーク強度を適当な内部標準ピーク（エチレン－スチレン－ジビニルベンゼン共重合体に由来する適当なピーク）を用いて比較する。ここで、クロス共重合体のジビニルベンゼン単位のビニル基水素（プロトン）のピーク強度（面積）が、エチレン－スチレン－ジビニルベンゼン共重合体マクロモノマーのジビニルベンゼン単位の同ピーク強度（面積）と比較して５０％未満、好ましくは２０％未満である。アニオン重合（クロス化工程）の際にスチレンの重合と同時にジビニルベンゼンも共重合し、エチレン－スチレン－ジビニルベンゼン共重合体鎖とポリスチレン鎖がジビニルベンゼン単位を介して結合されるために、アニオン重合後のクロス共重合体ではジビニルベンゼン単位のビニル基の水素（プロトン）のピーク強度は大きく減少する。実際にはジビニルベンゼン単位のビニル基の水素（プロトン）のピークはアニオン重合後のクロス共重合体では実質的に消失している。詳細は公知文献「ジビニルベンゼンユニットを含有するオレフィン系共重合体を用いた分岐型共重合体の合成」、荒井亨、長谷川勝、日本ゴム協会誌、ｐ３８２、ｖｏｌ．８２（２００９）に記載されている。 Hereinafter, the cross copolymer to be used in the present invention will be described. The present cross copolymer is a copolymer having an ethylene-aromatic vinyl compound-aromatic polyene copolymer chain derived from a macromonomer and an aromatic vinyl compound polymer chain, and an ethylene-aromatic vinyl compound-aromatic compound It is characterized by having a structure in which the polyene copolymer chain and the aromatic vinyl compound polymer chain are linked via an aromatic polyene monomer unit. The fact that the ethylene-aromatic vinyl compound-aromatic polyene copolymer chain and the aromatic vinyl compound polymer chain are linked via an aromatic polyene monomer unit can be proved by the following observable phenomenon. Here, an example in which a representative ethylene-styrene-divinylbenzene copolymer chain and a polystyrene chain are linked via a divinylbenzene unit is described. That is, 1H-NMR (proton NMR of proton-copolymer obtained through the anionic polymerization of the ethylene-styrene-divinylbenzene copolymer macromonomer obtained in the coordination polymerization process and the copolymer and styrene in the presence of the copolymer And the peak intensities of vinyl hydrogen (proton) of both divinylbenzene units are compared using appropriate internal standard peaks (appropriate peaks derived from ethylene-styrene-divinylbenzene copolymer). Here, the peak intensity (area) of the vinyl hydrogen (proton) of the divinylbenzene unit of the cross copolymer is compared with the peak intensity (area) of the divinylbenzene unit of the ethylene-styrene-divinylbenzene copolymer macromonomer. Less than 50%, preferably less than 20%. During the anionic polymerization (crossing step), divinylbenzene is also copolymerized simultaneously with the polymerization of styrene, and the ethylene-styrene-divinylbenzene copolymer chain and the polystyrene chain are linked via the divinylbenzene unit, so the anionic polymerization is performed. In the subsequent cross copolymer, the peak intensity of hydrogen (proton) of the vinyl group of the divinylbenzene unit is greatly reduced. In fact, the peak of hydrogen (proton) of the vinyl group of the divinylbenzene unit is substantially eliminated in the cross copolymer after anionic polymerization. Details are described in the well-known literature "Synthesis of branched copolymer using olefin copolymer containing divinylbenzene unit", Arai Akira, Hasegawa Masaru, Japan Rubber Association Journal, p 382, vol. 82 (2009).
　別な観点から、クロス共重合体において、エチレン－芳香族ビニル化合物－芳香族ポリエン共重合体鎖と芳香族ビニル化合物重合体鎖が芳香族ポリエン単量体単位を介して結合している（一例としてエチレン－スチレン－ジビニルベンゼン共重合体鎖とポリスチレン鎖がジビニルベンゼン単位を介して結合している）ことは、以下の観察可能な現象で証明できる。すなわち本クロス共重合体に対し、適当な溶媒を用いソックスレー抽出を十分な回数行った後においても、含まれるエチレン－スチレン－ジビニルベンゼン共重合体鎖とポリスチレン鎖を分別することができない。通常、本クロス共重合体に含まれるエチレン－スチレン－ジビニルベンゼン共重合体鎖と同一組成のエチレン－スチレン－ジビニルベンゼン共重合体とポリスチレンは、沸騰アセトンによるソックスレー抽出を行うことで、アセトン不溶部としてエチレン－スチレン－ジビニルベンゼン共重合体に、アセトン可溶部としてポリスチレンに分別できる。しかし、本クロス共重合体に同様のソックスレー抽出を行った場合、アセトン可溶部として本クロス共重合体に含まれる比較的少量のポリスチレンホモポリマーが得られるが、大部分の量を占めるアセトン不溶部には、ＮＭＲ測定を行うことでエチレン－スチレン－ジビニルベンゼン共重合体鎖とポリスチレン鎖が共に含まれていることが示され、これらはソックスレー抽出で分別することができないことがわかる。これについてもその詳細は公知文献「ジビニルベンゼンユニットを含有するオレフィン系共重合体を用いた分岐型共重合体の合成」、荒井亨、長谷川勝、日本ゴム協会誌、ｐ３８２、ｖｏｌ．８２（２００９）に記載されている。 From another point of view, in the cross copolymer, the ethylene-aromatic vinyl compound-aromatic polyene copolymer chain and the aromatic vinyl compound polymer chain are linked via an aromatic polyene monomer unit (one example) The fact that the ethylene-styrene-divinylbenzene copolymer chain and the polystyrene chain are linked via a divinylbenzene unit) can be proved by the following observable phenomenon. That is, even after Soxhlet extraction is performed a sufficient number of times with the present cross copolymer using an appropriate solvent, the contained ethylene-styrene-divinylbenzene copolymer chain and polystyrene chain can not be separated. In general, ethylene-styrene-divinylbenzene copolymer having the same composition as the ethylene-styrene-divinylbenzene copolymer chain contained in the present cross copolymer and polystyrene are subjected to Soxhlet extraction with boiling acetone to obtain an acetone insoluble portion As ethylene-styrene-divinylbenzene copolymer, it can be fractionated into polystyrene as an acetone soluble part. However, when the same Soxhlet extraction is performed on the present cross copolymer, although a relatively small amount of polystyrene homopolymer contained in the present cross copolymer can be obtained as an acetone-soluble part, it is insoluble in acetone that occupies most of the amount. On the other hand, it is shown that the ethylene-styrene-divinylbenzene copolymer chain and the polystyrene chain are both contained in part by NMR measurement, and these can not be fractionated by Soxhlet extraction. The details of this are also known in the literature "Synthesis of branched copolymer using olefin copolymer containing divinylbenzene unit", Arai Akira, Hasegawa Masaru, Japan Rubber Association Journal, p 382, vol. 82 (2009).
　以上から本発明のクロス共重合体を規定する表現としては、クロス共重合体は、エチレン－芳香族ビニル化合物－芳香族ポリエン共重合体鎖と芳香族ビニル化合物重合体鎖を有し、エチレン－芳香族ビニル化合物－芳香族ポリエン共重合体鎖と芳香族ビニル化合物重合体鎖が芳香族ポリエン単量体単位を介して結合している構造を有する共重合体であることが好ましい。本クロス共重合体には、比較的少量の芳香族ビニル化合物（ポリスチレン）ホモポリマーが含まれていても良い。
　さらに好ましくは以下の（１）～（３）の条件をすべて満たす共重合体である。
（１）配位重合工程で得られるエチレン－芳香族ビニル化合物－芳香族ポリエン共重合体鎖の芳香族ビニル単量体単位の含量が５モル％以上３０モル％以下、好ましくは１０モル％以上３０モル％以下、芳香族ポリエン単量体単位の含量０．０１モル％以上０．２モル％以下、残部がエチレン単位の含量である。
（２）配位重合工程で得られるエチレン－芳香族ビニル化合物－芳香族ポリエン共重合体鎖の重量平均分子量が５万以上３０万以下、分子量分布（Ｍｗ／Ｍｎ）が１．８以上６以下である。
（３）クロス共重合体中に含まれるエチレン－芳香族ビニル化合物－芳香族ポリエン共重合体鎖の含量が５０質量％以上９５質量％以下の範囲にある。 From the above, as an expression defining the cross copolymer of the present invention, the cross copolymer has ethylene-aromatic vinyl compound-aromatic polyene copolymer chain and aromatic vinyl compound polymer chain, and ethylene- The copolymer is preferably a copolymer having a structure in which an aromatic vinyl compound-aromatic polyene copolymer chain and an aromatic vinyl compound polymer chain are linked via an aromatic polyene monomer unit. The present cross copolymer may contain a relatively small amount of an aromatic vinyl compound (polystyrene) homopolymer.
More preferably, they are copolymers satisfying all the following conditions (1) to (3).
(1) The content of the aromatic vinyl monomer unit of the ethylene-aromatic vinyl compound-aromatic polyene copolymer chain obtained in the coordination polymerization step is 5 mol% or more and 30 mol% or less, preferably 10 mol% or more The content is 30 mol% or less, the content of aromatic polyene monomer units is 0.01 mol% or more and 0.2 mol% or less, and the balance is the content of ethylene units.
(2) The weight average molecular weight of the ethylene-aromatic vinyl compound-aromatic polyene copolymer chain obtained in the coordination polymerization step is 50,000 to 300,000, and the molecular weight distribution (Mw / Mn) is 1.8 to 6 It is.
(3) The content of the ethylene-aromatic vinyl compound-aromatic polyene copolymer chain contained in the cross copolymer is in the range of 50% by mass to 95% by mass.
　さらに別な観点から、本クロス共重合体を説明する。本クロス共重合体は、配位重合工程とアニオン重合工程からなる重合工程を含む製造方法で得られ、配位重合工程として、シングルサイト配位重合触媒を用いてエチレン、芳香族ビニル化合物単量体および芳香族ポリエン単量体の共重合を行ってエチレン－芳香族ビニル化合物－芳香族ポリエン共重合体鎖を合成し、次にアニオン重合工程として、このエチレン－芳香族ビニル化合物－芳香族ポリエン共重合体鎖と芳香族ビニル化合物単量体の共存下、アニオン重合開始剤によるアニオン重合により製造される共重合体であることが好ましい。アニオン重合工程において使用される芳香族ビニル化合物単量体としては、配位重合工程で重合液中に残留する未反応モノマーを用いても、これに新たに芳香族ビニル化合物モノマーを添加しても良い。重合液へのアニオン重合開始剤の添加により、アニオン重合が開始されるが、この場合、重合液中にエチレン－芳香族ビニル化合物－芳香族ポリエン共重合体鎖の芳香族ポリエン単量体単位と比較し、圧倒的に多く含まれる芳香族ビニル化合物単量体から実質的にアニオン重合が開始し、芳香族ビニル単量体を重合しながら、エチレン－芳香族ビニル化合物－芳香族ポリエン共重合体鎖の芳香族ポリエン単量体単位のビニル基も共重合しつつ、重合は進行する。そのため、得られるクロス共重合体は、公知文献及び当業者の知識からは、主鎖であるエチレン－芳香族ビニル化合物－芳香族ポリエン共重合体鎖とクロス鎖である芳香族ビニル化合物重合体鎖がグラフトスルー形式で結合した構造（交差結合）が多く含まれると考えられる。以上からクロス共重合体を規定する表現としては、エチレン－芳香族ビニル化合物－芳香族ポリエン共重合体鎖と芳香族ビニル化合物重合体鎖のグラフトスルー共重合体であることが好ましい。 The present cross copolymer will be described from another viewpoint. The present cross copolymer is obtained by a manufacturing method including a polymerization step consisting of a coordination polymerization step and an anion polymerization step, and a single site coordination polymerization catalyst is used as the coordination polymerization step, and a single amount of ethylene or aromatic vinyl compound is used. The ethylene-aromatic vinyl compound-aromatic polyene copolymer chain is synthesized by copolymerizing a monomer and an aromatic polyene monomer, and then this ethylene-aromatic vinyl compound-aromatic polyene is synthesized as an anionic polymerization step. It is preferable that it is a copolymer manufactured by anion polymerization by an anion polymerization initiator in the coexistence of a copolymer chain and an aromatic vinyl compound monomer. As the aromatic vinyl compound monomer used in the anionic polymerization step, either an unreacted monomer remaining in the polymerization solution in the coordination polymerization step or an aromatic vinyl compound monomer may be newly added to this good. An anionic polymerization is initiated by the addition of an anionic polymerization initiator to the polymerization solution, but in this case, the aromatic polyene monomer unit of the ethylene-aromatic vinyl compound-aromatic polyene copolymer chain is added to the polymerization solution and In comparison, an anionic polymerization substantially starts from an aromatic vinyl compound monomer contained in an overwhelmingly large amount, and an ethylene-aromatic vinyl compound-aromatic polyene copolymer is obtained while the aromatic vinyl monomer is polymerized. The polymerization proceeds while the vinyl group of the aromatic polyene monomer unit of the chain is also copolymerized. Therefore, the cross copolymer obtained is known to those skilled in the art and known in the art, the ethylene-aromatic vinyl compound-aromatic polyene copolymer chain as the main chain and the aromatic vinyl compound polymer chain as the cross chain It is considered that a large number of structures (cross bonds) bonded in a graft-through manner are included. From the above, the expression for defining the cross copolymer is preferably a graft-through copolymer of an ethylene-aromatic vinyl compound-aromatic polyene copolymer chain and an aromatic vinyl compound polymer chain.
　芳香族ビニル化合物単量体としては、スチレンおよび各種の置換スチレン、例えばｐ－メチルスチレン、ｍ－メチルスチレン、ｏ－メチルスチレン、ｏ－ｔ－ブチルスチレン、ｍ－ｔ－ブチルスチレン、ｐ－ｔ－ブチルスチレン、ｐ－クロロスチレン、ｏ－クロロスチレン等の各スチレン系単量体に由来する単量体が挙げられる。工業的には好ましくはスチレン、ｐ－メチルスチレン、ｐ－クロロスチレン、特に好ましくはスチレンが用いられる。これら芳香族ビニル化合物単量体は、１種類でもよく２種類以上の併用であってもよい。 As the aromatic vinyl compound monomer, styrene and various substituted styrenes such as p-methylstyrene, m-methylstyrene, o-methylstyrene, o-t-butylstyrene, m-t-butylstyrene, pt And monomers derived from each styrenic monomer such as -butylstyrene, p-chlorostyrene, o-chlorostyrene and the like. Industrially preferably, styrene, p-methylstyrene, p-chlorostyrene, particularly preferably styrene are used. These aromatic vinyl compound monomers may be used alone or in combination of two or more.
　芳香族ポリエン単量体とは、１０以上３０以下の炭素数を持ち、複数の二重結合（ビニル基）と単数または複数の芳香族基を有し、二重結合（ビニル基）の１つが配位重合に用いられて重合した状態であっても残りの二重結合がアニオン重合可能な芳香族ポリエンである。好ましくは、オルトジビニルベンゼン、パラジビニルベンゼン及びメタジビニルベンゼンのいずれか１種または２種以上の混合物が好適に用いられる。 The aromatic polyene monomer has a carbon number of 10 or more and 30 or less, has a plurality of double bonds (vinyl group) and one or more aromatic groups, and one of the double bonds (vinyl group) is Even when used in coordination polymerization, the remaining double bonds are anionically polymerizable aromatic polyenes. Preferably, any one or a mixture of two or more of ortho divinylbenzene, paradivinylbenzene and metadivinylbenzene is suitably used.
　クロス共重合体及びその製造方法の詳細は、その全体の記載をそれぞれ出典明示によりここに援用する、ＷＯ２０００／３７５１７号、ＷＯ２００７／１３９１１６号、または特開２００９－１２０７９２号公報に記載されている。 The details of the cross copolymer and the method for producing the same are described in WO 2000/37517, WO 2007/139116, or JP 2009-120792 A, the entire description of which is incorporated herein by reference.
　本発明の導電性樹脂組成物には必要に応じて、さらにポリエチレン系樹脂を添加してもよい。その添加量は、好ましくは前記熱可塑性樹脂１００質量部に対し１～３０質量部である。ポリエチレン系樹脂としては、特に限定されないが、エチレン－メタクリル酸エステル共重合体、エチレン－アクリル酸エステル共重合体、エチレン－アクリル酸共重合体、エチレン－メタクリル酸共重合体、低密度ポリエチレン樹脂（ＬＤＰＥ）、高密度ポリエチレン樹脂（ＨＤＰＥ）、直鎖状低密度ポリエチレン樹脂（ＬＬＤＰＥ）に代表されるポリエチレン系樹脂を使用するのが好ましい。 If necessary, a polyethylene resin may be further added to the conductive resin composition of the present invention. The addition amount thereof is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the thermoplastic resin. The polyethylene-based resin is not particularly limited, but ethylene-methacrylic acid ester copolymer, ethylene-acrylic acid ester copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, low density polyethylene resin ( It is preferable to use a polyethylene resin represented by LDPE), high density polyethylene resin (HDPE), and linear low density polyethylene resin (LLDPE).
　ポリエチレン系樹脂のメルトフローインディックスは、１９０℃、荷重２．１６ｋｇ（ＪＩＳ－Ｋ－７２１０に準じ測定）で０．１ｇ／１０分以上が好ましい。ポリエチレン系樹脂を添加することで、カーボンブラックの脱離をさらに低減させることが可能になる。添加量が１質量部未満ではその効果が不十分であり、３０質量部を越えるとポリスチレン系樹脂、ＡＢＳ系樹脂中に均一に分散させることが困難となり、効果が発現しない場合がある。 The melt flow index of the polyethylene resin is preferably 0.1 g / 10 min or more at 190 ° C. and a load of 2.16 kg (measured in accordance with JIS-K-7210). The addition of the polyethylene-based resin makes it possible to further reduce the desorption of carbon black. If the addition amount is less than 1 part by mass, the effect is insufficient, and if it exceeds 30 parts by mass, it may be difficult to uniformly disperse in the polystyrene resin and the ABS resin, and the effect may not be exhibited.
　本発明の導電性樹脂組成物は、十分な成形加工性を維持するために、表面固有抵抗値が１０２～１０１０Ωとなるようにカーボンブラックを充填した場合、メルトフローインディックス（ＪＩＳ－Ｋ－７２１０に準じて測定）が、ポリスチレン系樹脂の場合、２００℃、荷重５ｋｇの条件で、ＡＢＳ系樹脂の場合、２２０℃、荷重１０ｋｇの条件で、それぞれ、０．１ｇ／１０分以上であることが好ましい。また、本導電性樹脂組成物は、電子部品包装容器として適当な引張弾性率、破断点強度、耐折強度を有する。具体的には、いずれもＭＤ方向で、引張弾性率として、おおむね１０００ＭＰａ以上３０００ＭＰａ以下、破断点強度２５ＭＰａ以上５０ＭＰａ以下、耐折強度として１００回以上、好ましくは３００回以上である。 The conductive resin composition of the present invention, when filled with carbon black so as to have a surface specific resistance value of 10 2 to 10 10 Ω, in order to maintain sufficient moldability, melt flow index (JIS- Measured according to K-7210) at a temperature of 200 ° C. under a load of 5 kg in the case of polystyrene-based resin, and at a temperature of 220 ° C. under a load of 10 kg under 0.1 g / 10 min. Is preferred. In addition, the present conductive resin composition has a tensile modulus of elasticity, a breaking point strength and a bending resistance suitable as an electronic component packaging container. Specifically, in all, in the MD direction, the tensile modulus is about 1000 MPa or more and 3000 MPa or less, the breaking point strength is 25 MPa or more and 50 MPa or less, and the bending resistance is 100 times or more, preferably 300 times or more.
　本発明の導電性樹脂組成物には、必要に応じて組成物の流動特性および成形品の力学特性を改善するために、滑剤、可塑剤、加工助剤、補強剤、安定剤など、通常樹脂に用いられる各種添加剤や他の樹脂成分を添加することが可能である。 The conductive resin composition of the present invention is usually a resin, such as a lubricant, a plasticizer, a processing aid, a reinforcing agent, a stabilizer, etc., in order to improve the flow characteristics of the composition and the mechanical properties of the molded article, if necessary. It is possible to add various additives and other resin components used in
　本発明において、原料を混練、ペレット化し樹脂組成物を得るためには、バンバリーミキサー、押出機等の公知の方法を用いることができる。混練の順序は任意であり、混練に際しては、原料を一括して混練することも可能であるし、また例えば、クロス共重合体とカーボンブラック、熱可塑性樹脂とクロス共重合体の混合物を別々に混練し、その混練物を最後に一括して混練するといった様に段階的に混練することも可能である。 In the present invention, in order to knead and pelletize the raw materials to obtain a resin composition, known methods such as a Banbury mixer and an extruder can be used. The order of kneading is arbitrary, and it is also possible to knead the raw materials together at the time of kneading, or, for example, a mixture of a cross copolymer and carbon black, and a mixture of a thermoplastic resin and a cross copolymer separately. It is also possible to knead in stages, such as kneading and finally knead | mixing the kneaded material collectively.
　本発明の導電性樹脂組成物は、良好な力学物性や成形加工性を示し、さらに、接触や摩擦によるカーボンブラックの脱離が非常に少ないという点で、電子部品包装容器として好適に使用できる。本導電性樹脂組成物は、任意の公知の方法で成形し、電子部品包装容器として好適に用いることが出来る。電子部品包装容器とは電子部品の包装容器であるが、例えば射出成型や、シート状に成形したものを真空成形、圧空成形、熱板成形等の公知の方法によりトレー、マガジンチューブ、キャリアテープ（エンボスキャリアテープ）等の電子部品包装容器として用いることが出来る。特にキャリアテープ、トレーに好適に用いられる。電子部品包装容器に電子部品を収納することにより電子部品包装体となる。この場合容器には必要に応じ蓋がされる。例えばキャリアテープについては、電子部品を収納した後にカバーテープによる蓋が施される。電子部品包装体にはこのようなものも含む。 The conductive resin composition of the present invention exhibits good mechanical properties and moldability, and can be suitably used as an electronic component packaging container in that the detachment of carbon black due to contact or friction is very small. The conductive resin composition can be molded by any known method and suitably used as an electronic component packaging container. The electronic component packaging container is a packaging container for electronic components, for example, a tray, a magazine tube, a carrier tape (in a known method such as injection molding, vacuum forming, pressure forming, hot plate forming etc.) It can be used as an electronic component packaging container such as embossed carrier tape). In particular, it is suitably used for carrier tapes and trays. An electronic component package is obtained by housing the electronic component in the electronic component packaging container. In this case, the container is capped if necessary. For example, in the case of a carrier tape, a lid with a cover tape is provided after housing the electronic component. An electronic component package includes such a thing.
　導電性樹脂組成物のシートとしては単層のシート、多層のシートがある。多層のシートとは熱可塑性樹脂からなる基材層の少なくとも片面に導電性樹脂組成物の層を有するものである。基材層の熱可塑性樹脂は特に限定されないが、例えばポリスチレン系樹脂、ＡＢＳ系樹脂、ポリカーボネート系樹脂等を使用することができ、好ましくはポリスチレン系樹脂及びＡＢＳ系樹脂から選ばれる一種以上を使用する。基材層の熱可塑性樹脂は、本発明の導電性樹脂組成物に用いられる熱可塑性樹脂と同じ樹脂であることが、層間の接着性という観点からは好ましい。シートの肉厚は０．１～３．０ｍｍであることが好ましく、多層のシートにおいては、全体の肉厚に占める導電性樹脂組成物の層の肉厚は２％～８０％とするとよい。 The sheet of the conductive resin composition may be a single layer sheet or a multilayer sheet. A multilayer sheet is one having a layer of a conductive resin composition on at least one side of a substrate layer made of a thermoplastic resin. The thermoplastic resin of the base material layer is not particularly limited, but for example, polystyrene resin, ABS resin, polycarbonate resin and the like can be used, preferably one or more selected from polystyrene resin and ABS resin is used . The thermoplastic resin of the base material layer is preferably the same resin as the thermoplastic resin used for the conductive resin composition of the present invention, from the viewpoint of the adhesiveness between the layers. The thickness of the sheet is preferably 0.1 to 3.0 mm, and in the case of a multilayer sheet, the thickness of the layer of the conductive resin composition in the entire thickness may be 2% to 80%.
　電子部品としては特に限定されず、例えば、ＩＣ、抵抗、コンデンサ、インダクタ、トランジスタ、ダイオード、ＬＥＤ（発光ダイオード）、液晶、圧電素子レジスター、フィルター、水晶発振子、水晶振動子、コネクター、スイッチ、ボリュウム、リレー等がある。ＩＣの形式にも特に限定されず、例えばＳＯＰ、ＨＥＭＴ、ＳＱＦＰ、ＢＧＡ、ＣＳＰ、ＳＯＪ、ＱＦＰ、ＰＬＣＣ等がある。 The electronic component is not particularly limited, and, for example, an IC, a resistor, a capacitor, an inductor, a transistor, a diode, an LED (light emitting diode), a liquid crystal, a piezoelectric element resistor, a filter, a quartz oscillator, a quartz oscillator, a connector, a switch, a volume , Relay etc. There are no particular limitations on the type of IC, and examples include SOP, HEMT, SQFP, BGA, CSP, SOJ, QFP, PLCC, and the like.
　以下、本発明を実施例によりさらに説明するが、本発明はこれらに限定されるものではない。
　実施例、比較例に用いた原料樹脂、製法は以下の通りである。 Hereinafter, the present invention will be further described by way of examples, but the present invention is not limited thereto.
The raw material resin used for the Example and the comparative example and the manufacturing method are as follows.
　評価は以下の方法によって実施した。 The evaluation was performed by the following method.
＜表面固有抵抗値＞
　三菱ケミカルアナリティック社製ロレスターＧＸ、ＭＣＰを用いて、端子間距離を１０ｍｍとし、シートを巾方向に等間隔に１０箇所、表裏各２列計４０箇所の表面抵抗値を測定し、対数平均値を表面固有抵抗値とした。 <Surface resistivity>
Using Lorester GX and MCP manufactured by Mitsubishi Chemical Analytics, the distance between the terminals is 10 mm, and the sheet resistance is measured at 10 locations at equal intervals in the width direction, and 40 locations on each of the front and back lines. Was taken as the surface specific resistance value.
＜引張特性＞
　ＪＩＳ－Ｋ－７１２７に準拠して、４号試験片を使用しインストロン型引張試験機により１０ｍｍ／ｍｉｎの引張速度で引張試験を行い、流れ方向と幅方向の測定値の平均を評価結果とした。 <Tensile characteristics>
In accordance with JIS-K-7127, a tensile test is carried out at a tensile speed of 10 mm / min using an Instron type tensile tester using No. 4 test pieces, and the average of measured values in the flow direction and width direction is evaluated did.
＜カーボン脱離性＞
　真空成形により得られた２０ｍｍ×３０ｍｍのトレーシートの中にＱＦＰ１４ｍｍ×２０ｍｍ×６４ｐｉｎのＩＣを挿入し、ストローク２０ｍｍで２０万回往復振動させた後ＩＣのリード部へのカーボンブラック等黒色付着物の有無をマイクロスコープで観察した。評価は４個のＩＣに対し下記基準で５段階評価を行いその合計を結果とした。２０点満点。本発明においては、１５点以上が好ましい。
１：リード全部のシートに接していた部分全体に付着がある
２：リード全部に付着がみられる
３：２１～６３個に付着がみられる
４：付着のあるリードが２０個以下である
５：全く付着がみられない <Carbon releasability>
Insert a QFP 14 mm x 20 mm x 64 pin IC into a 20 mm x 30 mm tray sheet obtained by vacuum forming, and reciprocate for 200,000 cycles with a stroke of 20 mm, and then deposit black deposits such as carbon black on IC leads. The presence or absence was observed with a microscope. Evaluation performed five-step evaluation with the following reference | standard with respect to four IC, and made the total the result. 20 points full marks. In the present invention, 15 or more points are preferable.
1: Adherence is observed on the entire part in contact with the whole sheet of the leads 2: Adherence is observed on all the leads 3: 21 to 63 Adherence is observed 4: 4: Adherent leads are 20 or less 5: No adhesion is seen
＜耐折強度＞
　ＪＩＳ－Ｐ－８１１５に準拠し速度１７５ｒ．ｐ．ｍ．、折り曲げ角度１３５度、荷重５００ｇで評価を行った。 <Bending resistance>
According to JIS-P-8115, the speed 175r. p. m. The evaluation was performed at a bending angle of 135 degrees and a load of 500 g.
＜熱可塑性樹脂＞
　用いた熱可塑性樹脂は以下の通りである。
　ポリスチレン：東洋スチレン社製　ＨＲＭ－１２
　耐衝撃性ポリスチレン樹脂（ＨＩＰＳ）：東洋スチレン社製　ＨＩ－Ｅ４
　ＡＢＳ：デンカ株式会社製　デンカＡＢＳ　ＳＥ－１０ <Thermoplastic resin>
The thermoplastic resin used is as follows.
Polystyrene: Toyo Styrene HRM-12
Impact-resistant polystyrene resin (HIPS): Toyo Styrene Co. HI-E4
ABS: Denka Co., Ltd. Denka ABS SE-10
＜カーボンブラック＞
　用いたカーボンブラックはデンカ株式会社製、デンカブラック粒状品である。 <Carbon black>
The carbon black used is Denka Black granular product manufactured by Denka Co., Ltd.
＜クロス共重合体＞
　下記クロス共重合体１～３を使用した。
　これらのクロス共重合体は、ＷＯ２０００／３７５１７号、ＷＯ２００７／１３９１１６号、特開２００９－１２０７９２号公報記載の実施例あるいは比較例の製造方法で製造したもので、下記組成は、同様にこれら公報記載の方法で求めた。なお、クロス共重合体を規定するために、用いられるエチレン－スチレン－ジビニルベンゼン共重合体のスチレン含量、ジビニルベンゼン含量、重量平均分子量（Ｍｗ）、分子量分布（Ｍｗ／Ｍｎ）、クロス共重合体中のエチレン－スチレン－ジビニルベンゼン共重合体の含量、ポリスチレン鎖の重量平均分子量（Ｍｗ）、分子量分布（Ｍｗ／Ｍｎ）を示す。 <Cross Copolymer>
The following cross copolymers 1 to 3 were used.
These cross copolymers are produced by the production methods of Examples or Comparative Examples described in WO 2000/37517, WO 2007/139116, and JP 2009-120792 A, and the following compositions are similarly described in these publications. It asked by the method of. The styrene content, divinylbenzene content, weight average molecular weight (Mw), molecular weight distribution (Mw / Mn), cross copolymer of ethylene-styrene-divinylbenzene copolymer used to define the cross copolymer The content of ethylene-styrene-divinylbenzene copolymer, the weight average molecular weight (Mw) of polystyrene chains, and the molecular weight distribution (Mw / Mn) are shown.
クロス共重合体１　
　・エチレン－スチレン－ジビニルベンゼン共重合体のスチレン含量１６モル％、ジビニルベンゼン含量０．０８３モル％、重量平均分子量１０００００、分子量分布２．３、
　・エチレン－スチレン－ジビニルベンゼン共重合体の含量：８３質量％、
　・ポリスチレン鎖の重量平均分子量２８０００、分子量分布１．２
　・Ａ硬度７４ Cross copolymer 1
-Styrene content of ethylene-styrene-divinylbenzene copolymer: 16 mol%, divinylbenzene content: 0.083 mol%, weight average molecular weight: 100,000, molecular weight distribution: 2.3,
· Content of ethylene-styrene-divinylbenzene copolymer: 83% by mass,
・ Polystyrene chain weight average molecular weight 28,000, molecular weight distribution 1.2
・ A hardness 74
クロス共重合体２　
　・エチレン－スチレン－ジビニルベンゼン共重合体のスチレン含量２５モル％、ジビニルベンゼン含量０．０７０モル％、重量平均分子量１１５０００、分子量分布２．２、
　・エチレン－スチレン－ジビニルベンゼン共重合体の含量：８３質量％、
　・ポリスチレン鎖の重量平均分子量１８０００、分子量分布１．２
　・Ａ硬度６４ Cross copolymer 2
-Styrene content of ethylene-styrene-divinylbenzene copolymer 25 mol%, divinylbenzene content 0.070 mol%, weight average molecular weight 115000, molecular weight distribution 2.2,
· Content of ethylene-styrene-divinylbenzene copolymer: 83% by mass,
・ Polystyrene chain weight average molecular weight 18,000, molecular weight distribution 1.2
・ A hardness 64
クロス共重合体３　
　・エチレン－スチレン－ジビニルベンゼン共重合体のスチレン含量２０モル％、ジビニルベンゼン含量０．０６５モル％、重量平均分子量１６１０００、分子量分布２．５、
　・エチレン－スチレン－ジビニルベンゼン共重合体の含量：８４質量％、
　・ポリスチレン鎖の重量平均分子量１８０００、分子量分布１．２
　・Ａ硬度５６ Cross copolymer 3
-Styrene content of ethylene-styrene-divinylbenzene copolymer 20 mol%, divinylbenzene content 0.065 mol%, weight average molecular weight 161000, molecular weight distribution 2.5,
-Content of ethylene-styrene-divinylbenzene copolymer: 84% by mass,
・ Polystyrene chain weight average molecular weight 18,000, molecular weight distribution 1.2
・ A hardness 56
＜ポリエチレン系樹脂＞
　・ＥＥＡ（エチレン－エチルアクリレート樹脂）：ＮＵＣコポリマーＤＰＤＪ－６１６９（日本ユニカー社製）
　・ＨＤＰＥ（高密度ポリエチレン樹脂）ハイゼックス５０００Ｈ（プライムポリマー社製） <Polyethylene resin>
EEA (ethylene-ethyl acrylate resin): NUC copolymer DPDJ-6169 (manufactured by Nippon Unicar Co., Ltd.)
・ HDPE (high density polyethylene resin) HYZEX 5000H (manufactured by Prime Polymer Co.)
＜ＳＥＢＳ＞
　・ＳＥＢＳ（水素添加スチレン－ブタジエン共重合体樹脂）Ａ：タフテックＨ－１０５２（旭化成社製） <SEBS>
SEBS (hydrogenated styrene-butadiene copolymer resin) A: Tuftec H-1052 (manufactured by Asahi Kasei Corporation)
＜ＥＶＡ＞
　・ＥＶ－２６０（三井－デュポンポリケミカル社製） <EVA>
・ EV-260 (Mitsui-made by DuPont Polychemicals)
＜導電性樹脂組成物および単層シートの作成＞
　原料組成割合にて各々計量し、高速混合機により均一混合した後、φ４５ｍｍベント式二軸押出機を用いて混練し、ストランドカット法によりペレット化し導電性樹脂組成物を得た。次にペレット化した樹脂組成物をφ６５ｍｍ押出機（Ｌ／Ｄ＝２８）とＴダイを用いて厚さ３００μｍのシート状に成形した。得られたシートを真空成形しＱＦＰ１４ｍｍ×２０ｍｍ／６４ｐｉｎのＩＣ包装用真空成形トレー及び同エンボスキャリアテープを得た。 <Preparation of conductive resin composition and single layer sheet>
Each of the raw material composition ratios was weighed, uniformly mixed by a high speed mixer, and then kneaded using a φ45 mm vent type twin screw extruder, and pelletized by a strand cut method to obtain a conductive resin composition. Next, the pelletized resin composition was formed into a sheet having a thickness of 300 μm using a φ65 mm extruder (L / D = 28) and a T-die. The obtained sheet was vacuum formed to obtain a QFP 14 mm × 20 mm / 64 pin vacuum formed tray for IC packaging and the same embossed carrier tape.
　実施例、比較例の配合および評価結果を表１に示す。 The formulations and evaluation results of the examples and comparative examples are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
＜多層シートの作成＞
　さらに、実施例８記載の導電性樹脂組成物を用い、基材層にＡＢＳ樹脂（デンカ株式会社製　デンカＡＢＳ　ＳＥ－１０）を用い、φ６５ｍｍ押出機と２台のφ４０ｍｍ押出機を使用しフィードブロック法により全体の厚みが３００μｍで、導電性樹脂組成物の層を基材層の両面に各３０μｍの厚さで積層したシートを製造した。本多層シートの表面固有抵抗値は、６×１０４Ωであった。この多層のシートをヒータープレートにより接触加熱した後圧空にて成形する熱成形法にてキャリアテープとし、ＩＣの包装に好適に用いる事ができた。前記に準じてカーボン脱離性試験を行ったところ、評価合計点数は１７点であった。 <Creating multi-layer sheet>
Furthermore, using the conductive resin composition described in Example 8, using a ABS resin (Denka ABS SE-10 manufactured by Denka Co., Ltd.) for the base layer, using a φ65 mm extruder and two φ40 mm extruders, a feed block According to the method, a sheet having a total thickness of 300 μm and a layer of the conductive resin composition laminated on both sides of the base layer with a thickness of 30 μm was produced. The surface specific resistance value of this multilayer sheet was 6 × 10 4 Ω. The multi-layered sheet was heated by contact with a heater plate and then compressed and formed into a carrier tape by a thermoforming method, and could be suitably used for packaging of an IC. When the carbon releasability test was conducted according to the above, the total evaluation score was 17 points.
　本発明の導電性樹脂組成物は、良好な力学物性（引張弾性率、破断点強度、耐折強度）と適切な範囲の表面抵抗値を示しつつ、非常に良好なカーボン脱離性（低いカーボン脱離性）を示す。そのため、電子部品包装容器用の材料として好適である。 The conductive resin composition of the present invention exhibits very good carbon releasability (low carbon while showing good mechanical properties (tensile elastic modulus, breaking strength, bending resistance) and surface resistance values in an appropriate range. Releasability). Therefore, it is suitable as a material for electronic component packaging containers.

Claims (10)

  1. 熱可塑性樹脂１００質量部に対し、カーボンブラック５～６０質量部、クロス共重合体１０～１００質量部を含有し、その表面固有抵抗値が１０２～１０１０Ωである導電性樹脂組成物。 A conductive resin composition containing 5 to 60 parts by mass of carbon black and 10 to 100 parts by mass of a cross copolymer with respect to 100 parts by mass of a thermoplastic resin and having a surface resistivity of 10 2 to 10 10 Ω.
  2. 前記熱可塑性樹脂が、ポリスチレン系樹脂及びＡＢＳ樹脂から選ばれる一種以上である、請求項１記載の導電性樹脂組成物。 The conductive resin composition according to claim 1, wherein the thermoplastic resin is one or more selected from a polystyrene resin and an ABS resin.
  3. 前記クロス共重合体が、エチレン－芳香族ビニル化合物－芳香族ポリエン共重合体鎖と芳香族ビニル化合物重合体鎖を有する共重合体であり、エチレン－芳香族ビニル化合物－芳香族ポリエン共重合体鎖と芳香族ビニル化合物重合体鎖が芳香族ポリエン単量体単位を介して結合する構造を有しており、かつ以下の（１）～（３）の条件を満足する共重合体である、請求項１または２に記載の導電性樹脂組成物。
    （１）エチレン－芳香族ビニル化合物－芳香族ポリエン共重合体鎖の芳香族ビニル化合物単量体単位の含量が５モル％以上３０モル％以下、芳香族ポリエン単量体単位の含量が０．０１モル％以上０．２モル％以下、残部がエチレン単量体単位の含量である。
    （２）エチレン－芳香族ビニル化合物－芳香族ポリエン共重合体鎖の重量平均分子量が５万以上３０万以下、分子量分布（Ｍｗ／Ｍｎ）が１．８以上６以下である。
    （３）クロス共重合体中に含まれるエチレン－芳香族ビニル化合物－芳香族ポリエン共重合体鎖の含量が５０質量％以上９５質量％以下の範囲にある。     The cross copolymer is a copolymer having an ethylene-aromatic vinyl compound-aromatic polyene copolymer chain and an aromatic vinyl compound polymer chain, and an ethylene-aromatic vinyl compound-aromatic polyene copolymer A copolymer having a structure in which a chain and an aromatic vinyl compound polymer chain are linked via an aromatic polyene monomer unit, and satisfying the following conditions (1) to (3), The conductive resin composition according to claim 1.
    (1) The content of the aromatic vinyl compound monomer unit of the ethylene-aromatic vinyl compound-aromatic polyene copolymer chain is 5 mol% or more and 30 mol% or less, and the content of the aromatic polyene monomer unit is 0. 01 mol% or more and 0.2 mol% or less, the balance is the content of ethylene monomer units.
    (2) The weight average molecular weight of the ethylene-aromatic vinyl compound-aromatic polyene copolymer chain is 50,000 or more and 300,000 or less, and the molecular weight distribution (Mw / Mn) is 1.8 or more and 6 or less.
    (3) The content of the ethylene-aromatic vinyl compound-aromatic polyene copolymer chain contained in the cross copolymer is in the range of 50% by mass to 95% by mass.
  4. さらにポリエチレン系樹脂を、前記熱可塑性樹脂１００質量部に対し１～３０質量部含む、請求項１～３のいずれか一項に記載の導電性樹脂組成物。 The conductive resin composition according to any one of claims 1 to 3, further comprising 1 to 30 parts by mass of a polyethylene resin relative to 100 parts by mass of the thermoplastic resin.
  5. 請求項１～４のいずれか一項に記載の導電性樹脂組成物を用いた電子部品包装容器。 An electronic component packaging container using the conductive resin composition according to any one of claims 1 to 4.
  6. 請求項１～４のいずれか一項に記載の導電性樹脂組成物を用いた電子部品包装体。 An electronic component package using the conductive resin composition according to any one of claims 1 to 4.
  7. 請求項１～４のいずれか一項に記載の導電性樹脂組成物を用いたシート。 A sheet using the conductive resin composition according to any one of claims 1 to 4.
  8. ポリスチレン系樹脂及びＡＢＳ系樹脂から選ばれた少なくとも１種類の熱可塑性樹脂からなる基材層の、少なくとも片面に請求項１～４のいずれか一項記載の導電性樹脂組成物を積層した多層シート。 A multilayer sheet in which the conductive resin composition according to any one of claims 1 to 4 is laminated on at least one surface of a base material layer comprising at least one thermoplastic resin selected from polystyrene resins and ABS resins. .
  9. 請求項７又は８に記載のシートを用いた電子部品包装容器。 The electronic component packaging container using the sheet | seat of Claim 7 or 8.
  10. 請求項７又は８に記載のシートを用いた電子部品包装体。 An electronic component package using the sheet according to claim 7 or 8.
PCT/JP2018/032286 2017-09-01 2018-08-31 Electroconductive resin composition WO2019045030A1 (en)

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