WO2014097360A1 - Resin composition for semiconductor integrated circuit device packaging tray and semiconductor integrated circuit device packaging tray - Google Patents

Resin composition for semiconductor integrated circuit device packaging tray and semiconductor integrated circuit device packaging tray Download PDF

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Publication number
WO2014097360A1
WO2014097360A1 PCT/JP2012/008165 JP2012008165W WO2014097360A1 WO 2014097360 A1 WO2014097360 A1 WO 2014097360A1 JP 2012008165 W JP2012008165 W JP 2012008165W WO 2014097360 A1 WO2014097360 A1 WO 2014097360A1
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Prior art keywords
component
weight
parts
integrated circuit
resin composition
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PCT/JP2012/008165
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French (fr)
Japanese (ja)
Inventor
敬文 太田
拓也 首藤
正博 雛田
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東京インキ株式会社
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Priority to PCT/JP2012/008165 priority Critical patent/WO2014097360A1/en
Publication of WO2014097360A1 publication Critical patent/WO2014097360A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/28—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection
    • H01L23/29—Encapsulations, e.g. encapsulating layers, coatings, e.g. for protection characterised by the material, e.g. carbon
    • H01L23/293—Organic, e.g. plastic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/40—Polyamides containing oxygen in the form of ether groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/44—Polyester-amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/005—Modified block copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/12—Polyester-amides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Definitions

  • the present invention relates to a resin composition for a semiconductor integrated circuit device packaging tray and a semiconductor integrated circuit device packaging tray.
  • a semiconductor integrated circuit device packaging tray for storing and transferring a semiconductor integrated circuit is used.
  • a resin composition used for such a tray a resin composition containing a polyphenylene ether resin is known (see, for example, Patent Document 1).
  • the inventors added a predetermined amount of talc to a specific type of resin component and used a predetermined amount of an antistatic agent having a specific structure, thereby improving heat resistance, impact resistance, and electrostatic discharge prevention performance. It has been found that a tray with excellent balance can be obtained.
  • the deflection temperature under load (load 1.8 MPa) measured according to ISO75 is 160 ° C. or higher.
  • the Charpy impact strength value measured according to ISO179 is 5 kJ / m 2 or higher. Resistance value is less than 10 10 ⁇ / ⁇
  • a semiconductor integrated circuit device packaging tray using the above-described resin composition for a semiconductor integrated circuit device packaging tray can also be provided.
  • a resin composition for a semiconductor integrated circuit device packaging tray and a semiconductor integrated circuit device packaging tray capable of producing a tray excellent in balance of heat resistance, impact resistance and electrostatic discharge prevention performance.
  • the resin composition for a semiconductor integrated circuit device packaging tray of the present embodiment (hereinafter sometimes referred to as a resin composition)
  • E A polyether block polymer, which contains at least one of a block polymer of polyether and polyolefin, and a polyether ester amide.
  • the resin (E) content in this resin composition is 7 to 15 parts by weight with respect to 100 parts by weight as a total of component (A), component (B), component (C) and component (D). It is a composition. Furthermore, the molded product obtained from the resin composition satisfies the following requirements.
  • (A) Deflection temperature (load 1.8 MPa) measured according to ISO75 is 160 ° C. or higher
  • Charpy impact strength value measured according to ISO179 is 5 kJ / m 2 or more
  • Surface specific Resistance value is less than 10 10 ⁇ / ⁇
  • the polyphenylene ether resin has a structural unit represented by the following general formula (1).
  • R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, a halogen atom, a primary or secondary alkyl group, a phenyl group, a hydrocarbon oxy group, or a haloalkyl group. And any one of cyano groups, n is an integer indicating the degree of polymerization (excluding 0).)
  • R 1 and R 2 are alkyl groups or phenyl groups, particularly alkyl groups having 1 to 4 carbon atoms
  • R 3 and R 4 are hydrogen atoms. Or a copolymer is preferable.
  • polyphenylene ether resin examples include poly (2,6-dimethyl-1,4-phenylene ether), poly (2,6-diethyl-1,4-phenylene ether), and poly (2,6-dipropyl-1). , 4-phenylene ether), poly (2-ethyl-6-methyl-1,4-phenylene ether), poly (2-methyl-6-propyl-1,4-phenylene ether), poly-2-methyl-6 -Isopropyl-1,4-phenylene ether, poly-2,6-dimethoxy-1,4-phenylene ether, poly-2,6-dichloromethyl-1,4-phenylene ether, poly-2,6-diphenyl -1,4-phenylene ether, poly-2,6-dinitrile-1,4-phenylene ether, poly-2,6-dichloro-1,4-phenylene ether, poly-2,5-dimethyl-1 , 4-Henille Any one or more of ether, and the
  • poly (2,6-dimethyl-1,4-phenylene ether) is particularly preferable from the viewpoint of heat resistance.
  • the polyphenylene ether resin may be alloyed with other resins such as polystyrene.
  • the polyphenylene ether resin preferably has an intrinsic viscosity at 25 ° C. measured in chloroform of 0.36 to 0.46 dl / g as a weighted average.
  • a plurality of polyphenylene ether resins having different intrinsic viscosities may be used in combination. When a plurality of different intrinsic viscosities are used in combination, the value of the intrinsic viscosity of each polyphenylene ether resin is preferably 0.35 to 0.46 dl / g.
  • the content of the polyphenylene ether resin in the resin composition for a semiconductor integrated circuit device packaging tray is preferably 40 parts by weight or more when the total of the resin components (components (A) to (C)) is 100 parts by weight. Moreover, it is preferable that it is 95 weight part or less. Heat resistance can be improved by setting it as 40 weight part or more.
  • the content of the polyphenylene ether resin is preferably 70 parts by weight or more when the total resin component is 100 parts by weight.
  • the fluidity at the time of heat melting of the resin composition can be ensured by setting it to 95 parts by weight or less, and particularly 90 parts by weight or less.
  • polystyrene resin In this embodiment, polystyrene is an optional component.
  • the polystyrene resin is a vinyl aromatic polymer represented by the following general formula (2), a copolymer with another vinyl monomer that can be copolymerized, or a copolymer with a rubber polymer. .
  • the component (B) since the component (B) is not a styrene elastomer, the component (B) does not include the styrene elastomer of the component (C).
  • the polystyrene resin contains 50% by weight or more of the aromatic vinyl monomer unit represented by the general formula (2).
  • R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • Z represents hydrogen, an alkyl group having 1 to 4 carbon atoms or halogen
  • x represents 0 to 5 Indicates an integer
  • Specific examples of the aromatic vinyl monomer include styrene, ⁇ -methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, p-tert-butyl.
  • Examples thereof include styrene and ethylstyrene, and examples of the polystyrene resin include homopolymerization or copolymerization of these monomers.
  • Other compounds copolymerizable with aromatic vinyl monomers include methacrylic acid esters such as methyl methacrylate and ethyl methacrylate, unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile, and acids such as maleic anhydride. Any of an anhydride etc. is mentioned.
  • a copolymer with methacrylic acid esters or acid anhydrides as the polystyrene resin, and in particular, glycidyl (meth) alkylate and a styrene monomer. It is preferable not to contain a copolymer.
  • the copolymer of the vinyl aromatic polymer and the rubbery polymer described above include, for example, rubber-modified polystyrene (high impact polystyrene: HIPS), which is a styrene-butadiene copolymer, from the viewpoint of impact resistance. Any of rubber-modified styrene-acrylonitrile copolymer (ABS resin) is preferable. However, they do not exhibit the properties as an elastomer, ie, rubber elasticity.
  • the content of the polystyrene resin in the resin composition for a semiconductor integrated circuit device packaging tray is 0 to 20 parts by weight with respect to 100 parts by weight of the component (A). Especially, it is preferable that it is 10 weight part or more with respect to 100 weight part of component (A), Furthermore, it is 15 weight part or more. Moreover, the resistance value at the time of manufacturing a semiconductor integrated circuit device packaging tray can be made low by setting it as 20 weight part or less. On the other hand, impact resistance can be ensured by setting it as 10 weight part or more.
  • Styrenic elastomers exhibit rubber elasticity at room temperature.
  • Styrene elastomers include styrene / butadiene / styrene block copolymer (SBS), styrene / isoprene / styrene block copolymer (SIS), styrene / ethylene / butylene / styrene block copolymer (SEBS), and styrene / ethylene / propylene block copolymer (SEP). 1) or more thermoplastic elastomers.
  • SEBS is preferable because of its excellent heat resistance.
  • a styrene elastomer modified with an acid anhydride such as maleic anhydride is preferable, and among them, an acid-modified styrene / butylene / modified with an acid anhydride such as maleic anhydride.
  • Styrene block copolymer SEBS is preferred.
  • the content of the styrene-based elastomer in the resin composition for a semiconductor integrated circuit device packaging tray is preferably 3 parts by weight or more and 12 parts by weight or less with respect to 100 parts by weight of the component (A).
  • Impact resistance can be improved by setting it as 3 weight part or more.
  • heat resistance is securable by setting it as 12 weight part or less, especially 9 weight part or less.
  • the resin composition of the present invention contains 35 parts by weight or more and 70 parts by weight or less of talc with respect to 100 parts by weight of the component (A). Especially, it is preferable to contain 50 weight part or more of talc with respect to 100 weight part of component (A). By containing 35 parts by weight or more of talc, the heat resistance and dimensional stability of the molded product can be ensured. Moreover, impact resistance can be ensured by setting the content of talc to 70 parts by weight or less. Furthermore, the extrusion at the time of shaping
  • the talc is not particularly limited, but may be treated with a surface treatment agent such as a silane coupling agent or a titanate coupling agent.
  • the average particle diameter (d50) of talc is preferably 2 to 15 ⁇ m.
  • the component (E) is a polyether block polymer, and includes at least one of a block polymer of polyether and polyolefin and a polyether ester amide.
  • component (E) Peletron PVH (trade name), Peletron MP (trade name), Peletron HS (trade name), Peletron H (trade name), Peletron P (trade name) (all are Sanyo Chemical Industries, Ltd.)
  • Peletron PVH trade name
  • Peletron MP trade name
  • Peletron HS trade name
  • Peletron H trade name
  • Peletron P trade name
  • This component (E) preferably has a resistance value of less than 1 ⁇ 10 7 ⁇ / ⁇ .
  • the resistance value can be measured by pressing the component (E) at 220 ° C., adjusting the humidity at 23 ° C. and 50% RH for 24 hours, and then measuring with a surface resistance meter (ST-4, manufactured by SIMCO JAPAN).
  • the component (E) preferably has a resistance value of 5 ⁇ 10 6 ⁇ / ⁇ or less.
  • the lower limit value of the resistance value of the component (E) is not particularly limited, but is, for example, 1 ⁇ 10 4 ⁇ / ⁇ .
  • polyether examples include polyether diol, polyether diamine, and modified products thereof.
  • Polyether diol has a structure obtained by addition reaction of alkylene oxide (hereinafter sometimes abbreviated as AO) to diol, and has a general formula: H— (OA 1) m —O—E 1 —O— ( A1O) m'-H.
  • E1 represents a residue obtained by removing a hydroxyl group from a diol
  • A1 represents an alkylene group having 2 to 4 carbon atoms (hereinafter abbreviated as C)
  • m and m ′ represent the number of alkylene oxides added per hydroxyl group of the diol. .
  • n (OA1) and m ′ (A1O) may be the same or different, and when they are composed of two or more oxyalkylene groups, the bonding form is block or random or these Any combination of these may be used.
  • m and m ′ are generally integers of 1 to 300, preferably 2 to 250, more preferably 10 to 100.
  • M and m ′ may be the same or different.
  • diol examples include dihydric alcohols (for example, C2-12 aliphatic, alicyclic and aromatic ring-containing dihydric alcohols), C6-18 dihydric phenols, and tertiary amino group-containing diols.
  • dihydric alcohols for example, C2-12 aliphatic, alicyclic and aromatic ring-containing dihydric alcohols
  • C6-18 dihydric phenols examples include tertiary amino group-containing diols.
  • aliphatic dihydric alcohol examples include alkylene glycol (ethylene glycol, propylene glycol (hereinafter abbreviated as EG and PG, respectively)), 1,4-butanediol, 1,6-hexanediol, neopentyl glycol (hereinafter 1 each).
  • alicyclic dihydric alcohol examples include cyclohexanedimethanol;
  • aromatic ring-containing dihydric alcohol examples include xylylene diol.
  • dihydric phenol examples include monocyclic dihydric phenols (hydroquinone, catechol, resorcin, urushiol, etc.), bisphenols (bisphenol A, -F and -S, 4,4'-dihydroxydiphenyl-2,2-butane, Dihydroxybiphenyl and the like) and condensed polycyclic divalent phenols (dihydroxynaphthalene, binaphthol and the like).
  • monocyclic dihydric phenols hydroquinone, catechol, resorcin, urushiol, etc.
  • bisphenols bisphenol A, -F and -S, 4,4'-dihydroxydiphenyl-2,2-butane, Dihydroxybiphenyl and the like
  • condensed polycyclic divalent phenols condensed polycyclic divalent phenols
  • Examples of the tertiary amino group-containing diol include C1-12 aliphatic or alicyclic primary monoamines (methylamine, ethylamine, 1- and 2-propylamine, hexylamine, decylamine, dodecylamine, cyclopropylamine, And any one of cyclohexylamines such as cyclohexylamine and bishydroxyalkylated products of C6-12 aromatic ring-containing primary monoamines (aniline, benzylamine, etc.).
  • an aliphatic dihydric alcohol or bisphenol is preferred, and more preferred is either EG (ethylene glycol) or bisphenol A.
  • Polyether diol can be produced by addition reaction of alkylene oxide (AO) to diol.
  • alkylene oxide examples include C2-4 alkylene oxide [ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3- and 1,3-butylene oxide (hereinafter abbreviated as EO, PO, and BO, respectively).
  • EO, PO, and BO 1,3-butylene oxide
  • AO AO
  • C5-12 ⁇ -olefin, styrene Oxide and epihalohydrin (such as epichlorohydrin) can be used in a small proportion (for example, 30% or less based on the weight of total AO).
  • the coupling form may be random and / or block.
  • Preferred as AO is EO alone or a combination of EO and another AO (random and / or block addition).
  • the addition number of AO is usually an integer of 1 to 300, preferably 2 to 250, more preferably 10 to 100 per hydroxyl group of the diol.
  • Alkylene oxide (AO) can be added by a known method, for example, at a temperature of 100 to 200 ° C. in the presence of an alkali catalyst.
  • the polyether diamine has the general formula: H 2 N—A 2 — (OA 1) m —O—E 1 —O— (A 1 O) m′-A 2 —NH 2 (wherein the symbols E 1, A 1, m and m ′ are A2 is a C2-4 alkylene group, and A1 and A2 may be the same or different.
  • the polyether diamine can be obtained by changing the hydroxyl group of the polyether diol to an amino group by a known method, for example, by reducing the terminal obtained by cyanoalkylating the hydroxyl group of the polyether diol to an amino group Can be used. For example, it can be produced by reacting polyether diol with acrylonitrile and hydrogenating the resulting cyanoethylated product.
  • modified product examples include polyether diol or polyether diamine aminocarboxylic acid modified product (terminal amino group), the same isocyanate modified product (terminal isocyanate group) and the same epoxy modified product (terminal epoxy group).
  • the aminocarboxylic acid-modified product can be obtained by reacting polyether diol or polyether diamine with aminocarboxylic acid or lactam.
  • Polyolefins constituting the block polymer of polyether and polyolefin include polyolefins having carbonyl groups (preferably carboxyl groups, the same shall apply hereinafter) at both ends of the polymer, polyolefins having hydroxyl groups at both ends of the polymer, and amino groups. Can be used, such as polyolefin having both at both ends of the polymer and polyolefin having isocyanate groups at both ends of the polymer.
  • a polyolefin having a carbonyl group at one end of the polymer a polyolefin having a hydroxyl group at one end of the polymer, a polyolefin having an amino group at one end of the polymer, a polyolefin having an isocyanate group at one end of the polymer, etc.
  • a polyolefin having a carbonyl group and a polyolefin having a carbonyl group at one end of the polymer are preferable because of easy modification.
  • the polyether ester amide is, for example, a copolymer of polyamide having carboxyl groups at both ends and polyether diol.
  • examples of the polyamide include one or more of a ring-opening polymer of lactam and a self-polymer of aminocarboxylic acid.
  • the resin composition of the present invention contains 7 to 15 parts by weight of component (E) in total with respect to 100 parts by weight of component (A), component (B), component (C) and component (D). .
  • component (E) By setting it as 7 weight part or more, the surface resistance value of a molded article can be made low.
  • heat resistance can be ensured by setting it as 15 weight part or less.
  • the component (A), the component (B), the component (C), and the component (D) are added to the component ( It is preferable to contain 10 parts by weight or more of E) in total.
  • the surface resistance value when the amount of the antistatic agent added in the resin composition is increased, the surface resistance value can be lowered, but the heat resistance is inferior. On the other hand, when the addition amount of the antistatic agent is lowered, the surface resistance value is increased.
  • the content of the component (D) is set to a predetermined amount, and the component (E) having a specific structure is used to reduce the content of the component (E) to the component (A) and the component ( B) With respect to a total of 100 parts by weight of component (C) and component (D), even if the value is as low as 15 parts by weight or less, the surface resistance value can be reduced and the heat resistance is excellent. can do.
  • the resin composition of the present invention may have other additives such as pigments, dyes, fillers (glass fibers, mica, silica, etc.) depending on the purpose as long as the physical properties are not impaired. Further, an antioxidant may be included, a weathering agent, a lubricant, a release agent, and the like.
  • the resin composition of the present invention preferably does not contain a conductive filler such as conductive carbon black. By not containing a conductive filler, molding processability can be ensured, and further, coloring of the material can be prevented from being limited. It also prevents dirt from falling off the carbon.
  • the method for producing the resin composition of the present invention is not particularly limited, but a melt mixing method is desirable.
  • the injection molded product obtained from the resin composition for a semiconductor integrated circuit device packaging tray as described above satisfies the following requirements.
  • A Deflection temperature (load 1.8 MPa) measured according to ISO75 is 160 ° C. or higher (however, a test of 4 mm (thickness) ⁇ 10 mm (width) ⁇ 80 mm (length) by a method according to ISO179) Measurement using a piece)
  • B A test piece having a Charpy impact strength value measured in accordance with ISO 179 of 5 kJ / m 2 or more (however, a test piece of 4 mm (thickness) ⁇ 10 mm (width) ⁇ 80 mm (length) by a method in accordance with ISO 179) Measure using (C) Surface resistivity is less than 10 10 ⁇ / ⁇ Therefore, it is possible to provide a resin composition for a semiconductor integrated circuit device packaging tray capable of producing a tray excellent in balance of heat resistance, impact resistance, and electrostatic discharge prevention performance.
  • a molded article is manufactured as follows.
  • the resin composition is melt-kneaded using a twin screw extruder at an extrusion temperature of 300 ° C. and a rotation speed of 150 rpm to obtain pellets.
  • a test piece having a predetermined thickness is manufactured by injection molding using the pellets under conditions of a set temperature of 300 ° C. and a mold temperature of 120 ° C.
  • the physical properties (a) to (c) are measured.
  • the test piece is heated at 155 ° C. for 5 hours and left in a constant temperature and humidity chamber (23 ° C., 50% HR) for 24 hours, and then the measurement of (a) is performed.
  • a semiconductor integrated circuit device packaging tray having desired performance can be obtained by using the resin composition as described above and performing extrusion molding, injection molding, or the like.
  • the upper limit value of the deflection temperature under load (a) is not particularly limited, but is 200 ° C., for example.
  • the upper limit value of the Charpy impact strength of (b) is not particularly limited, but is 10 kJ / m 2 .
  • the lower limit value of the surface specific resistance value of (c) is not particularly limited, but is, for example, 1 ⁇ 10 4 ⁇ / ⁇ .
  • PPE-C Intrinsic viscosity (measured in chloroform at 25 ° C.) 0.45 dl / g poly (2,6-dimethyl-1,4-phenylene ether), trade name: LXR045, Bluestar New chemicals materials Co., Ltd.
  • PPE viscosity indicates a weighted average, and the viscosity of each PPE is the weight ratio of each PPE to the total PPE. Was the thing, is added value.
  • (C) Styrenic elastomer SEBS-A styrene / ethylene / butylene / styrene block copolymer, trade name: Tuftec H1041G, SEBS-B manufactured by Asahi Kasei Chemicals Corporation: maleic anhydride modified styrene / ethylene / butylene / styrene block copolymer, product Name: Tuftec M1911, manufactured by Asahi Kasei Chemicals Corporation
  • E Polyether block polymer E-1: Trade name: Peletron HS, manufactured by Sanyo Chemical Industries, Ltd., polyamide copolymer (resistance value 4 ⁇ 10 6 ⁇ / ⁇ )
  • E-2 Trade name: Peletron MP, manufactured by Sanyo Chemical Industries, Ltd., polyamide copolymer (resistance value 8 ⁇ 10 5 ⁇ / ⁇ )
  • Each of E-1 and E-2 includes at least one of a block polymer of polyether and polyolefin and polyether ester amide.
  • the resistance value was measured as follows. The component (E) was press-molded at 220 ° C., conditioned at 23 ° C. and 50% RH for 24 hours, and then measured with a surface resistance meter (ST-4, manufactured by SIMCO JAPAN).
  • Irgastat P18 polyetheresteramide composition
  • BASF Japan Ltd. resistance value 6 ⁇ 10 7 ⁇ / ⁇
  • entilla ethylene unsaturated carboxylic acid copolymer
  • Mitsui DuPont Polychemical Co., Ltd. resistance value 7 ⁇ 10 7 ⁇ / ⁇
  • Tables 1 and 2 components (B), (C), and (D) indicate ratios (parts by weight) to 100 parts by weight of component (A), and component (E) includes components (A) to (A). The ratio (part by weight) when the total of D) is 100 parts by weight is shown.
  • Example 1 Pellets (resin composition) having the composition shown in Table 1 were prepared. Specifically, PPE-A (component (A)) 30.0 parts by weight, PPE-C (component (A)) 70.0 parts by weight, HIPS (component (B)) 18.0 parts by weight, SEBS- B (component (C)) 9.0 parts by weight, E-2 (component (E)) 10 parts by weight, talc (component (D)) 55.0 parts by weight using a twin screw extruder, extrusion temperature Melt kneading was performed at 300 ° C. and a rotation speed of 150 rpm to obtain pellets. Next, this pellet was used for injection molding under the conditions of a preset temperature of 300 ° C. and a mold temperature of 120 ° C. The following test was implemented about the obtained molded article (test piece). The test results are shown in Table 1. Similarly, a tray molded product was obtained.
  • Charpy impact strength (Edgewise Impact, with notch) was measured according to ISO179 under the following conditions. Units of measurement are kJ / m 2. Test piece type: 4 mm (thickness) x 10 mm (width) x 80 mm (length) Notch type; Type A Load; 2J Temperature: 25 ° C
  • Examples 2 to 13 With the formulation shown in Table 1, pellets were obtained in the same manner as in Example 1. And the pellet was injection-molded similarly to Example 1, and the test piece was created. Similarly, a tray molded product was obtained. Further, the test was performed in the same manner as in Example 1.
  • the Charpy impact strength is 5 kJ / m 2 or more
  • the deflection temperature under load is 160 ° C. or more
  • the surface resistance value is less than 1 ⁇ 10 10 ⁇ / ⁇
  • the impact resistance, heat resistance, and surface resistance value are improved. It was excellent. Further, it was found that the appearance is particularly good when an acid-modified styrene elastomer is used.
  • Comparative Example 1 since the content of the component (E) was small, the surface resistance value was high.
  • the heat resistance was low because the content of component (E) was too large.
  • Comparative Examples 3 to 6 since an antistatic agent different from the component (E) was used, the surface resistance value was high.
  • Comparative Example 7 since the viscosity of the component (A) was too low, the impact resistance was poor. In Comparative Example 8, the content of the component (C) was too small, so that the impact resistance was poor. In comparative example 9, since there was too much content of a component (C), it became inferior to heat resistance. In comparative example 10, since there were too many components (B), it became inferior to heat resistance. In addition, Examples 1 to 13 were superior in balance of impact resistance, heat resistance, and surface resistance value to those disclosed in Patent Document 1.

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Abstract

The resin composition contains (A) polyphenylene ether resin, (B) 0-20 parts by weight of polystyrene resin per 100 parts by weight of component (A), (C) 3-12 parts by weight of styrene-based elastomer per 100 parts by weight of component (A), and (D) 35-70 parts by weight of talc per 100 parts by weight of component (A), contains (E) a block polymer of polyether and polyolefin which is a polyether-based block polymer and/or a polyetheresteramide, and the content of component (E) is 7-15 parts by weight per 100 total parts by weight of component (A), component (B), component (C), and component (D). A molded article also satisfies the following requirements. (a) The deflection temperature under load (load 1.8 MPa) measured according to ISO 75 is 160°C or greater, (b) the value of the Charpy impact strength measured according to ISO 179 is 5 kJ/m2 or greater, and (c) the surface resistivity value is less than 1010 Ω/□.

Description

半導体集積回路装置包装トレイ用樹脂組成物および半導体集積回路装置包装トレイResin composition for semiconductor integrated circuit device packaging tray and semiconductor integrated circuit device packaging tray
　本発明は、半導体集積回路装置包装トレイ用樹脂組成物および半導体集積回路装置包装トレイに関する。 The present invention relates to a resin composition for a semiconductor integrated circuit device packaging tray and a semiconductor integrated circuit device packaging tray.
　従来、半導体装置の製造過程においては、半導体集積回路を収納し、移送するための半導体集積回路装置包装トレイが使用されている。このようなトレイに使用される樹脂組成物としては、ポリフェニレンエーテル系樹脂を含む樹脂組成物が知られている（たとえば、特許文献１参照）。 Conventionally, in the manufacturing process of a semiconductor device, a semiconductor integrated circuit device packaging tray for storing and transferring a semiconductor integrated circuit is used. As a resin composition used for such a tray, a resin composition containing a polyphenylene ether resin is known (see, for example, Patent Document 1).
特開平７－２２８７６５号公報JP 7-228765 A
　半導体集積回路装置包装トレイは、半導体集積回路装置の加熱工程において使用されるため、高い耐熱性が求められる。また、半導体集積回路装置を確実に保護するためには、高い耐衝撃性が求められるとともに、静電気放電を防ぐ帯電防止性が要求される。
　近年、より厳しい環境下で、半導体集積回路装置包装トレイが使用されることとなったため、耐熱性、耐衝撃性、静電気放電防止性能のバランスに優れたものが求められているが、このような要求にこたえることができる樹脂組成物は開発されていなかった。 Since the semiconductor integrated circuit device packaging tray is used in the heating process of the semiconductor integrated circuit device, high heat resistance is required. Further, in order to reliably protect the semiconductor integrated circuit device, high impact resistance is required, and antistatic properties for preventing electrostatic discharge are required.
In recent years, since semiconductor integrated circuit device packaging trays have been used in more severe environments, there is a demand for a balance between heat resistance, impact resistance, and electrostatic discharge prevention performance. A resin composition that can meet the demand has not been developed.
　本発明者らは、特定種類の樹脂成分に対し、タルクを所定量添加するとともに、特定の構造を有する帯電防止剤を所定量使用することで、耐熱性、耐衝撃性、静電気放電防止性能のバランスに優れたトレイを得ることができることを見出した。
　すなわち、本発明によれば、
（Ａ）ポリフェニレンエーテル樹脂
（Ｂ）ポリスチレン樹脂（成分（Ｃ）を除く）を成分（Ａ）１００重量部に対して、０～２０重量部
（Ｃ）スチレン系エラストマーを成分（Ａ）１００重量部に対して、３～１２重量部
（Ｄ）タルクを成分（Ａ）１００重量部に対して、３５～７０重量部
を含むとともに、
（Ｅ）ポリエーテル系ブロックポリマーであり、ポリエーテルとポリオレフィンとのブロックポリマー、および、ポリエーテルエステルアミドのうちの少なくとも何れか一方を含み、
　成分（Ｅ）の含有量が成分（Ａ）と成分（Ｂ）と成分（Ｃ）と成分（Ｄ）との合計１００重量部に対し、７～１５重量部である樹脂組成物であり、
　当該樹脂組成物から得られる成形品が以下の要件を満たす半導体集積回路装置包装トレイ用樹脂組成物が提供される。
（ａ）ＩＳＯ７５に準拠して測定される荷重たわみ温度（荷重1.8ＭＰａ）が１６０℃以上
（ｂ）ＩＳＯ１７９に準拠して測定されるシャルピー衝撃強度の値が５ｋＪ／ｍ２以上
（ｃ）表面固有抵抗値が１０１０Ω／□未満
　また、本発明によれば、上述した半導体集積回路装置包装トレイ用樹脂組成物を使用した半導体集積回路装置包装トレイも提供できる。 The inventors added a predetermined amount of talc to a specific type of resin component and used a predetermined amount of an antistatic agent having a specific structure, thereby improving heat resistance, impact resistance, and electrostatic discharge prevention performance. It has been found that a tray with excellent balance can be obtained.
That is, according to the present invention,
(A) Polyphenylene ether resin (B) Polystyrene resin (excluding component (C)) with respect to 100 parts by weight of component (A) 0 to 20 parts by weight (C) 100 parts by weight of component (A) styrene elastomer 3 to 12 parts by weight (D) talc with respect to 100 parts by weight of component (A) and 35 to 70 parts by weight,
(E) a polyether block polymer, including at least one of a block polymer of polyether and polyolefin, and a polyether ester amide;
A resin composition in which the content of component (E) is 7 to 15 parts by weight with respect to 100 parts by weight in total of component (A), component (B), component (C) and component (D),
Provided is a resin composition for a semiconductor integrated circuit device packaging tray, in which a molded product obtained from the resin composition satisfies the following requirements.
(A) The deflection temperature under load (load 1.8 MPa) measured according to ISO75 is 160 ° C. or higher. (B) The Charpy impact strength value measured according to ISO179 is 5 kJ / m 2 or higher. Resistance value is less than 10 10 Ω / □ Further, according to the present invention, a semiconductor integrated circuit device packaging tray using the above-described resin composition for a semiconductor integrated circuit device packaging tray can also be provided.
　本発明によれば、耐熱性、耐衝撃性、静電気放電防止性能のバランスに優れたトレイを製造できる半導体集積回路装置包装トレイ用樹脂組成物および半導体集積回路装置包装トレイが提供される。 According to the present invention, there are provided a resin composition for a semiconductor integrated circuit device packaging tray and a semiconductor integrated circuit device packaging tray capable of producing a tray excellent in balance of heat resistance, impact resistance and electrostatic discharge prevention performance.
　以下、本発明の実施形態を説明する。
　本実施形態の半導体集積回路装置包装トレイ用樹脂組成物（以下、樹脂組成物ということもある）は、
（Ａ）ポリフェニレンエーテル樹脂
（Ｂ）ポリスチレン樹脂（成分（Ｃ）を除く）を成分（Ａ）１００重量部に対して、０～２０重量部
（Ｃ）スチレン系エラストマーを成分（Ａ）１００重量部に対して、３～１２重量部
（Ｄ）タルクを成分（Ａ）１００重量部に対して、３５～７０重量部
を含むとともに、
（Ｅ）ポリエーテル系ブロックポリマーであり、ポリエーテルとポリオレフィンとのブロックポリマー、および、ポリエーテルエステルアミドのうちの少なくとも何れか一方を含む。そして、この樹脂組成物における成分（Ｅ）含有量は成分（Ａ）と成分（Ｂ）と成分（Ｃ）と成分（Ｄ）との合計１００重量部に対し、７～１５重量部である樹脂組成物である。
　さらに、当該樹脂組成物から得られる成形品が以下の要件を満たす。
（ａ）ＩＳＯ７５に準拠して測定される荷重たわみ温度（荷重1.8ＭＰａ）が１６０℃以上
（ｂ）ＩＳＯ１７９に準拠して測定されるシャルピー衝撃強度の値が５ｋＪ／ｍ２以上
（ｃ）表面固有抵抗値が１０１０Ω／□未満 Embodiments of the present invention will be described below.
The resin composition for a semiconductor integrated circuit device packaging tray of the present embodiment (hereinafter sometimes referred to as a resin composition)
(A) Polyphenylene ether resin (B) Polystyrene resin (excluding component (C)) with respect to 100 parts by weight of component (A) 0 to 20 parts by weight (C) 100 parts by weight of component (A) styrene elastomer 3 to 12 parts by weight (D) talc with respect to 100 parts by weight of component (A) and 35 to 70 parts by weight,
(E) A polyether block polymer, which contains at least one of a block polymer of polyether and polyolefin, and a polyether ester amide. The resin (E) content in this resin composition is 7 to 15 parts by weight with respect to 100 parts by weight as a total of component (A), component (B), component (C) and component (D). It is a composition.
Furthermore, the molded product obtained from the resin composition satisfies the following requirements.
(A) Deflection temperature (load 1.8 MPa) measured according to ISO75 is 160 ° C. or higher (b) Charpy impact strength value measured according to ISO179 is 5 kJ / m 2 or more (c) Surface specific Resistance value is less than 10 10 Ω / □
（（Ａ）ポリフェニレンエーテル樹脂）
　ポリフェニレンエーテル樹脂は、以下の一般式（１）で示される構造単位を有する。 ((A) polyphenylene ether resin)
The polyphenylene ether resin has a structural unit represented by the following general formula (1).
Figure JPOXMLDOC01-appb-C000001
 （１）
Figure JPOXMLDOC01-appb-C000001
 (1)
（式（１）中、Ｒ１、Ｒ２、Ｒ３、Ｒ４はそれぞれ独立して水素原子、ハロゲン原子、第１級又は第２級のアルキル基、フェニル基、炭化水素オキシ基、ハロアルキル基、シアノ基のいずれかを示す。ｎは、重合度を示す整数（０を除く）である。）
　なかでも、耐熱性の観点から、Ｒ１、Ｒ２が、アルキル基又はフェニル基、特に炭素数が１～４個のアルキル基であり、Ｒ３、Ｒ４が水素原子であるポリフェニレンエーテル重合体又は共重合体が好ましい。
　ポリフェニレンエーテル樹脂の具体例としては、ポリ（２，６－ジメチル－１，４－フェニレンエーテル）、ポリ（２，６－ジエチル－１，４－フェニレンエーテル）、ポリ（２，６－ジプロピル－１，４－フェニレンエーテル）、ポリ（２－エチル－６－メチル－１，４－フェニレンエーテル）、ポリ（２－メチル－６－プロピル－１，４－フェニレンエーテル）、ポリ-２-メチル-６-イソプロピル-１，４-フエニレンエーテル、ポリ-２，６-ジメトキシ-１，４-フエニレンエーテル、ポリ-２，６-ジクロルメチル-１，４-フエニレンエーテル、ポリ-２，６-ジフエニル-１，４-フエニレンエーテル、ポリ-２，６-ジニトリル-１，４-フエニレンエーテル、ポリ-２，６-ジクロル-１，４-フエニレンエーテル、ポリ-２，５-ジメチル-１，４-フエニレンエーテル等のいずれか一種以上が挙げられる。
　なかでも、耐熱性の観点から、ポリ（２，６－ジメチル－１，４－フェニレンエーテル）が特に好ましい。
　なお、ポリフェニレンエーテル樹脂は、ポリスチレン等の他の樹脂とアロイ化されているものであってもよい。
　ポリフェニレンエーテル樹脂は、クロロホルム中で測定した２５℃の固有粘度が加重平均で０．３６～０．４６ｄｌ／ｇであることが好ましい。ポリフェニレンエーテル樹脂は、固有粘度の異なるものを複数組み合わせて使用してもよい。固有粘度が異なるものを複数組み合わせて使用する場合には、各ポリフェニレンエーテル樹脂の固有粘度の値が０．３５～０．４６ｄｌ／ｇであることが好ましい。
　ポリフェニレンエーテル樹脂の固有粘度の加重平均を０．４６ｄｌ／ｇ以下とすることで、樹脂組成物の成形が容易となる。一方で、ポリフェニレンエーテル樹脂の固有粘度の加重平均を０．３６ｄｌ／ｇ以上とすることで、成形品の耐衝撃性を向上させることができる。
　半導体集積回路装置包装トレイ用樹脂組成物におけるポリフェニレンエーテル樹脂の含有量は、樹脂成分（成分（Ａ）～（Ｃ））の合計を１００重量部とした場合、４０重量部以上であることが好ましく、また、９５重量部以下であることが好ましい。
　４０重量部以上とすることで、耐熱性を向上させることができる。ポリフェニレンエーテル樹脂の含有量は、樹脂成分の合計を１００重量部とした場合、なかでも、７０重量部以上とすることが好ましい。
　一方で、９５重量部以下、なかでも、９０重量部以下とすることで、樹脂組成物の熱溶融時の流動性を確保することができる。 (In formula (1), R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom, a halogen atom, a primary or secondary alkyl group, a phenyl group, a hydrocarbon oxy group, or a haloalkyl group. And any one of cyano groups, n is an integer indicating the degree of polymerization (excluding 0).)
Among these, from the viewpoint of heat resistance, R 1 and R 2 are alkyl groups or phenyl groups, particularly alkyl groups having 1 to 4 carbon atoms, and R 3 and R 4 are hydrogen atoms. Or a copolymer is preferable.
Specific examples of the polyphenylene ether resin include poly (2,6-dimethyl-1,4-phenylene ether), poly (2,6-diethyl-1,4-phenylene ether), and poly (2,6-dipropyl-1). , 4-phenylene ether), poly (2-ethyl-6-methyl-1,4-phenylene ether), poly (2-methyl-6-propyl-1,4-phenylene ether), poly-2-methyl-6 -Isopropyl-1,4-phenylene ether, poly-2,6-dimethoxy-1,4-phenylene ether, poly-2,6-dichloromethyl-1,4-phenylene ether, poly-2,6-diphenyl -1,4-phenylene ether, poly-2,6-dinitrile-1,4-phenylene ether, poly-2,6-dichloro-1,4-phenylene ether, poly-2,5-dimethyl-1 , 4-Henille Any one or more of ether, and the like.
Of these, poly (2,6-dimethyl-1,4-phenylene ether) is particularly preferable from the viewpoint of heat resistance.
The polyphenylene ether resin may be alloyed with other resins such as polystyrene.
The polyphenylene ether resin preferably has an intrinsic viscosity at 25 ° C. measured in chloroform of 0.36 to 0.46 dl / g as a weighted average. A plurality of polyphenylene ether resins having different intrinsic viscosities may be used in combination. When a plurality of different intrinsic viscosities are used in combination, the value of the intrinsic viscosity of each polyphenylene ether resin is preferably 0.35 to 0.46 dl / g.
By setting the weighted average of intrinsic viscosity of the polyphenylene ether resin to 0.46 dl / g or less, molding of the resin composition becomes easy. On the other hand, the impact resistance of the molded product can be improved by setting the weighted average of the intrinsic viscosity of the polyphenylene ether resin to 0.36 dl / g or more.
The content of the polyphenylene ether resin in the resin composition for a semiconductor integrated circuit device packaging tray is preferably 40 parts by weight or more when the total of the resin components (components (A) to (C)) is 100 parts by weight. Moreover, it is preferable that it is 95 weight part or less.
Heat resistance can be improved by setting it as 40 weight part or more. The content of the polyphenylene ether resin is preferably 70 parts by weight or more when the total resin component is 100 parts by weight.
On the other hand, the fluidity at the time of heat melting of the resin composition can be ensured by setting it to 95 parts by weight or less, and particularly 90 parts by weight or less.
（（Ｂ）ポリスチレン樹脂）
　本実施形態において、ポリスチレンは、任意の成分である。
　ポリスチレン樹脂は、以下の一般式（２）に示したビニル芳香族重合体、あるいは、共重合可能な他のビニル系単量体との共重合体またはゴム質重合体との共重合体である。ただし、本発明においては、成分（Ｂ）は、スチレン系エラストマーではないため、成分（Ｂ）は成分（Ｃ）のスチレン系エラストマーは含まない。
　ここで、ポリスチレン樹脂は、一般式（２）で表される芳香族ビニル系単量体単位５０重量％以上を含むものである。 ((B) polystyrene resin)
In this embodiment, polystyrene is an optional component.
The polystyrene resin is a vinyl aromatic polymer represented by the following general formula (2), a copolymer with another vinyl monomer that can be copolymerized, or a copolymer with a rubber polymer. . However, in the present invention, since the component (B) is not a styrene elastomer, the component (B) does not include the styrene elastomer of the component (C).
Here, the polystyrene resin contains 50% by weight or more of the aromatic vinyl monomer unit represented by the general formula (2).
Figure JPOXMLDOC01-appb-C000002
 （２）
Figure JPOXMLDOC01-appb-C000002
 (2)
（式（２）中、Ｒは、水素原子または、炭素原子数１～４のアルキル基を示し、Ｚは、水素、炭素数１～４のアルキル基またはハロゲンを示し、ｘは、０～５の整数を示す）
　芳香族ビニル系単量体の具体例としては、スチレン、α－メチルスチレン、２，４－ジメチルスチレン、モノクロロスチレン、ｏ－メチルスチレン、ｐ－メチルスチレン、ｍ－メチルスチレン、ｐ－ｔｅｒｔ－ブチルスチレン、エチルスチレン等のいずれかがあげられ、ポリスチレン樹脂としては、これらの単量体の単独重合あるいは、共重合が挙げられる。
　また、芳香族ビニル系単量体と共重合可能な他の化合物としてはメチルメタクリレート、エチルメタクリレート等のメタクリル酸エステル類、アクリロニトリル、メタクリロニトリルなどの不飽和ニトリル化合物類、無水マレイン酸等の酸無水物等のいずれかが挙げられる。
　ただし、耐熱性の観点からは、ポリスチレン樹脂としては、メタクリル酸エステル類や、酸無水物等との共重合体を使用しないことが好ましく、なかでも、（メタ）アルキル酸グリシジルとスチレン単量体との共重合体は含まないことが好ましい。
　また、前述したビニル芳香族重合体とゴム質重合体との共重合体としては、耐衝撃性の観点から、たとえば、スチレン－ブタジエン共重合体であるゴム変性ポリスチレン（ハイインパクトポリスチレン：ＨＩＰＳ）、ゴム変性スチレン－アクリロニトリル共重合体（ＡＢＳ樹脂）のいずれかが好ましい。ただし、これらはエラストマーとしての特性、すなわち、ゴム弾性は示さない。 (In the formula (2), R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, Z represents hydrogen, an alkyl group having 1 to 4 carbon atoms or halogen, and x represents 0 to 5 Indicates an integer)
Specific examples of the aromatic vinyl monomer include styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, p-tert-butyl. Examples thereof include styrene and ethylstyrene, and examples of the polystyrene resin include homopolymerization or copolymerization of these monomers.
Other compounds copolymerizable with aromatic vinyl monomers include methacrylic acid esters such as methyl methacrylate and ethyl methacrylate, unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile, and acids such as maleic anhydride. Any of an anhydride etc. is mentioned.
However, from the viewpoint of heat resistance, it is preferable not to use a copolymer with methacrylic acid esters or acid anhydrides as the polystyrene resin, and in particular, glycidyl (meth) alkylate and a styrene monomer. It is preferable not to contain a copolymer.
Examples of the copolymer of the vinyl aromatic polymer and the rubbery polymer described above include, for example, rubber-modified polystyrene (high impact polystyrene: HIPS), which is a styrene-butadiene copolymer, from the viewpoint of impact resistance. Any of rubber-modified styrene-acrylonitrile copolymer (ABS resin) is preferable. However, they do not exhibit the properties as an elastomer, ie, rubber elasticity.
　半導体集積回路装置包装トレイ用樹脂組成物におけるポリスチレン樹脂の含有量は、成分（Ａ）１００重量部に対して、０～２０重量部である。
　なかでも、成分（Ａ）１００重量部に対して、１０重量部以上、さらには、１５重量部以上であることが好ましい。
　また、２０重量部以下とすることで、半導体集積回路装置包装トレイを製造した場合の抵抗値を低くすることができる。
　一方で、１０重量部以上とすることで、耐衝撃性を確保することができる。 The content of the polystyrene resin in the resin composition for a semiconductor integrated circuit device packaging tray is 0 to 20 parts by weight with respect to 100 parts by weight of the component (A).
Especially, it is preferable that it is 10 weight part or more with respect to 100 weight part of component (A), Furthermore, it is 15 weight part or more.
Moreover, the resistance value at the time of manufacturing a semiconductor integrated circuit device packaging tray can be made low by setting it as 20 weight part or less.
On the other hand, impact resistance can be ensured by setting it as 10 weight part or more.
（（Ｃ）スチレン系エラストマー）
　スチレン系エラストマーは、常温でゴム弾性を示す。
　スチレン系エラストマーとしては、スチレン・ブタジエン・スチレンブロックコポリマー（ＳＢＳ）、スチレン・イソプレン・スチレンブロックコポリマー（ＳＩＳ）、スチレン・エチレン・ブチレン・スチレンブロックコポリマー（ＳＥＢＳ）、スチレン・エチレン・プロピレンブロックコポリマー（ＳＥＰ）等のいずれか１種以上の熱可塑性エラストマー挙げられる。なかでもＳＥＢＳは、耐熱性に優れており好ましい。
　また、成形品の外観の観点からは、無水マレイン酸等の酸無水物で変性されたスチレン系エラストマーが好ましく、なかでも、無水マレイン酸等の酸無水物で変性された酸変性スチレン・ブチレン・スチレンブロックコポリマー（ＳＥＢＳ）が好ましい。 ((C) Styrenic elastomer)
Styrenic elastomers exhibit rubber elasticity at room temperature.
Styrene elastomers include styrene / butadiene / styrene block copolymer (SBS), styrene / isoprene / styrene block copolymer (SIS), styrene / ethylene / butylene / styrene block copolymer (SEBS), and styrene / ethylene / propylene block copolymer (SEP). 1) or more thermoplastic elastomers. Among these, SEBS is preferable because of its excellent heat resistance.
Further, from the viewpoint of the appearance of the molded product, a styrene elastomer modified with an acid anhydride such as maleic anhydride is preferable, and among them, an acid-modified styrene / butylene / modified with an acid anhydride such as maleic anhydride. Styrene block copolymer (SEBS) is preferred.
　半導体集積回路装置包装トレイ用樹脂組成物におけるスチレン系エラストマーの含有量は、成分（Ａ）１００重量部に対して、３重量部以上、１２重量部以下であることが好ましい。３重量部以上とすることで、耐衝撃性を向上させることができる。また、１２重量部以下、特に９重量部以下とすることで、耐熱性を確保することができる。 The content of the styrene-based elastomer in the resin composition for a semiconductor integrated circuit device packaging tray is preferably 3 parts by weight or more and 12 parts by weight or less with respect to 100 parts by weight of the component (A). Impact resistance can be improved by setting it as 3 weight part or more. Moreover, heat resistance is securable by setting it as 12 weight part or less, especially 9 weight part or less.
（（Ｄ）タルク）
　本発明の樹脂組成物は、タルクを、成分（Ａ）１００重量部に対して、３５重量部以上、７０重量部以下含む。なかでも、タルクを成分（Ａ）１００重量部に対して、５０重量部以上含むことが好ましい。
　タルクを３５重量部以上含むことで、成形品の耐熱性および寸法安定性を確保することができる。また、タルクの含有量を７０重量部以下とすることで耐衝撃性を確保することができる。さらに、タルクの含有量を７０重量部以下とすることで、成形時の押し出しが容易となる。
　ここで、タルクとしては、特に制限されるものではないが、シラン系カップリング剤、チタネート系カップリング剤などの表面処理剤で処理されていてもよい。タルクの平均粒径（ｄ５０）としては、２～１５μｍのものが好ましい。 ((D) Talc)
The resin composition of the present invention contains 35 parts by weight or more and 70 parts by weight or less of talc with respect to 100 parts by weight of the component (A). Especially, it is preferable to contain 50 weight part or more of talc with respect to 100 weight part of component (A).
By containing 35 parts by weight or more of talc, the heat resistance and dimensional stability of the molded product can be ensured. Moreover, impact resistance can be ensured by setting the content of talc to 70 parts by weight or less. Furthermore, the extrusion at the time of shaping | molding becomes easy because content of talc shall be 70 weight part or less.
Here, the talc is not particularly limited, but may be treated with a surface treatment agent such as a silane coupling agent or a titanate coupling agent. The average particle diameter (d50) of talc is preferably 2 to 15 μm.
（成分（Ｅ）ポリエーテル系ブロックポリマー）
　成分（Ｅ）は、ポリエーテル系ブロックポリマーであり、ポリエーテルとポリオレフィンとのブロックポリマーおよびポリエーテルエステルアミドのうちの、少なくともいずれか一方を含む。
　たとえば、成分（Ｅ）として、ペレクトロンＰＶＨ（商品名）、ペレクトロンＭＰ（商品名）、ペレクトロンＨＳ（商品名）、ペレクトロンＨ（商品名）、ペレクトロンＰ（商品名）（いずれも三洋化成工業株式会社製）からなる群から選択される１種類以上を使用することができる。
　この成分（Ｅ）は、抵抗値が、１×１０７Ω/□未満であることが好ましい。抵抗値は、成分（Ｅ）を220℃でプレス成型し、23℃50%RHで24時間調湿後、表面抵抗計(SIMCO JAPAN株式会社製 ST-4)にて測定することで計測できる。
　なかでも、成分（Ｅ）は、抵抗値が、５×１０６Ω/□以下であることが好ましい。また、成分（Ｅ）の抵抗値の下限値は特に限定されないが、たとえば、１×１０４Ω/□である。 (Component (E) polyether block polymer)
The component (E) is a polyether block polymer, and includes at least one of a block polymer of polyether and polyolefin and a polyether ester amide.
For example, as component (E), Peletron PVH (trade name), Peletron MP (trade name), Peletron HS (trade name), Peletron H (trade name), Peletron P (trade name) (all are Sanyo Chemical Industries, Ltd.) One or more types selected from the group consisting of (manufactured) can be used.
This component (E) preferably has a resistance value of less than 1 × 10 7 Ω / □. The resistance value can be measured by pressing the component (E) at 220 ° C., adjusting the humidity at 23 ° C. and 50% RH for 24 hours, and then measuring with a surface resistance meter (ST-4, manufactured by SIMCO JAPAN).
Among them, the component (E) preferably has a resistance value of 5 × 10 6 Ω / □ or less. Further, the lower limit value of the resistance value of the component (E) is not particularly limited, but is, for example, 1 × 10 4 Ω / □.
　ポリエーテルとポリオレフィンとのブロックポリマーについて説明する。
　ポリエーテルとしては、ポリエーテルジオール、ポリエーテルジアミンおよびこれらの変性物のいずれかが挙げられる。 The block polymer of polyether and polyolefin will be described.
Examples of the polyether include polyether diol, polyether diamine, and modified products thereof.
　ポリエーテルジオールは、ジオールにアルキレンオキサイド（以下ＡＯと略記することもある）を付加反応させることにより得られる構造のものであり、一般式：Ｈ－（ＯＡ1）m－Ｏ－Ｅ1－Ｏ－（Ａ1Ｏ）m'－Ｈで示されるものが挙げられる。
  式中、Ｅ1はジオールから水酸基を除いた残基、Ａ1は炭素数（以下Ｃと略記）２～４のアルキレン基、ｍおよびｍ'はジオールの水酸基１個当たりのアルキレンオキサイドの付加数を表す。ｍ個の（ＯＡ1）とｍ'個の（Ａ1Ｏ）とは、同一でも異なっていてもよく、また、これらが２種以上のオキシアルキレン基で構成される場合の結合形式はブロックもしくはランダムまたはこれらの組合せのいずれでもよい。ｍおよびｍ'は、通常１～３００、好ましくは２～２５０、さらに好ましくは１０～１００の整数である。また、ｍとｍ'とは、同一でも異なっていてもよい。 Polyether diol has a structure obtained by addition reaction of alkylene oxide (hereinafter sometimes abbreviated as AO) to diol, and has a general formula: H— (OA 1) m —O—E 1 —O— ( A1O) m'-H.
In the formula, E1 represents a residue obtained by removing a hydroxyl group from a diol, A1 represents an alkylene group having 2 to 4 carbon atoms (hereinafter abbreviated as C), and m and m ′ represent the number of alkylene oxides added per hydroxyl group of the diol. . m (OA1) and m ′ (A1O) may be the same or different, and when they are composed of two or more oxyalkylene groups, the bonding form is block or random or these Any combination of these may be used. m and m ′ are generally integers of 1 to 300, preferably 2 to 250, more preferably 10 to 100. M and m ′ may be the same or different.
　ジオールとしては、２価アルコール（例えばＣ２～１２の脂肪族、脂環含有および芳香環含有２価アルコール）、Ｃ６～１８の２価フェノールおよび３級アミノ基含有ジオールのいずれかが挙げられる。
　脂肪族２価アルコールとしては、例えば、アルキレングリコール（エチレングリコール、プロピレングリコール（以下それぞれＥＧ、ＰＧと略記））、１，４－ブタンジオール、１，６－ヘキサンジオール、ネオペンチルグリコール（以下それぞれ１，４－ＢＤ、１，６－ＨＤ、ＮＰＧと略記）、１，１２－ドデカンジオールのいずれか；
　脂環含有２価アルコールとしては、例えば、シクロヘキサンジメタノール；
　芳香環含有２価アルコールとしては、例えば、キシリレンジオールが挙げられる。
　２価フェノールとしては、例えば、単環２価フェノール（ハイドロキノン、カテコール、レゾルシン、ウルシオール等）、ビスフェノール（ビスフェノールＡ、－Ｆおよび－Ｓ、４，４'－ジヒドロキシジフェニル－２，２－ブタン、ジヒドロキシビフェニル等）および縮合多環２価フェノール（ジヒドロキシナフタレン、ビナフトール等）のいずれかが挙げられる。 Examples of the diol include dihydric alcohols (for example, C2-12 aliphatic, alicyclic and aromatic ring-containing dihydric alcohols), C6-18 dihydric phenols, and tertiary amino group-containing diols.
Examples of the aliphatic dihydric alcohol include alkylene glycol (ethylene glycol, propylene glycol (hereinafter abbreviated as EG and PG, respectively)), 1,4-butanediol, 1,6-hexanediol, neopentyl glycol (hereinafter 1 each). , 4-BD, 1,6-HD, abbreviated as NPG), or 1,12-dodecanediol;
Examples of the alicyclic dihydric alcohol include cyclohexanedimethanol;
Examples of the aromatic ring-containing dihydric alcohol include xylylene diol.
Examples of the dihydric phenol include monocyclic dihydric phenols (hydroquinone, catechol, resorcin, urushiol, etc.), bisphenols (bisphenol A, -F and -S, 4,4'-dihydroxydiphenyl-2,2-butane, Dihydroxybiphenyl and the like) and condensed polycyclic divalent phenols (dihydroxynaphthalene, binaphthol and the like).
　３級アミノ基含有ジオールとしては、例えば、Ｃ１～１２の脂肪族または脂環含有１級モノアミン（メチルアミン、エチルアミン、１－および２－プロピルアミン、ヘキシルアミン、デシルアミン、ドデシルアミン、シクロプロピルアミン、シクロヘキシルアミン等のいずれか）のビスヒドロキシアルキル化物およびＣ６～１２の芳香環含有１級モノアミン（アニリン、ベンジルアミン等）のビスヒドロキシアルキル化物のいずれかが挙げられる。
  これらのうち帯電防止性の観点から好ましいのは、脂肪族２価アルコールおよびビスフェノールのいずれか、さらに好ましいのはＥＧ（エチレングリコール）およびビスフェノールＡのいずれかである。 Examples of the tertiary amino group-containing diol include C1-12 aliphatic or alicyclic primary monoamines (methylamine, ethylamine, 1- and 2-propylamine, hexylamine, decylamine, dodecylamine, cyclopropylamine, And any one of cyclohexylamines such as cyclohexylamine and bishydroxyalkylated products of C6-12 aromatic ring-containing primary monoamines (aniline, benzylamine, etc.).
Of these, from the viewpoint of antistatic properties, either an aliphatic dihydric alcohol or bisphenol is preferred, and more preferred is either EG (ethylene glycol) or bisphenol A.
　ポリエーテルジオールは、ジオールにアルキレンオキサイド（ＡＯ）を付加反応させることにより製造することができる。
　アルキレンオキサイドとしては、Ｃ２～４のアルキレンオキサイド［エチレンオキサイド、プロピレンオキサイド、１，２－、１，４－、２，３－および１，３－ブチレンオキサイド（以下それぞれＥＯ、ＰＯ、ＢＯと略記）のいずれか、およびこれらの２種以上の併用系が用いられるが、必要により他のＡＯまたは置換ＡＯ（以下、これらも含めてＡＯと総称する。）、例えばＣ５～１２のα－オレフィン、スチレンオキサイド、エピハロヒドリン（エピクロルヒドリン等）を少しの割合（例えば、全ＡＯの重量に基づいて３０％以下）で併用することもできる。
　２種以上のＡＯを併用するときの結合形式はランダムおよび／またはブロックのいずれでもよい。ＡＯとして好ましいのは、ＥＯ単独およびＥＯと他のＡＯとの併用（ランダムおよび／またはブロック付加）である。ＡＯの付加数は、ジオールの水酸基１個当り、通常１～３００、好ましくは２～２５０、さらに好ましくは１０～１００の整数である。 Polyether diol can be produced by addition reaction of alkylene oxide (AO) to diol.
Examples of the alkylene oxide include C2-4 alkylene oxide [ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3- and 1,3-butylene oxide (hereinafter abbreviated as EO, PO, and BO, respectively). And a combination system of two or more of these, if necessary, other AO or substituted AO (hereinafter collectively referred to as AO), for example, C5-12 α-olefin, styrene Oxide and epihalohydrin (such as epichlorohydrin) can be used in a small proportion (for example, 30% or less based on the weight of total AO).
When two or more kinds of AO are used in combination, the coupling form may be random and / or block. Preferred as AO is EO alone or a combination of EO and another AO (random and / or block addition). The addition number of AO is usually an integer of 1 to 300, preferably 2 to 250, more preferably 10 to 100 per hydroxyl group of the diol.
　アルキレンオキサイド（ＡＯ）の付加は、公知方法、例えばアルカリ触媒の存在下、１００～２００℃の温度で行なうことができる。 Alkylene oxide (AO) can be added by a known method, for example, at a temperature of 100 to 200 ° C. in the presence of an alkali catalyst.
　ポリエーテルジアミンは、一般式：Ｈ2Ｎ－Ａ2－（ＯＡ1）m－Ｏ－Ｅ1－Ｏ－（Ａ1Ｏ）m'－Ａ2－ＮＨ2（式中の記号Ｅ1，Ａ1、ｍおよびｍ'は前記と同様であり、Ａ2はＣ２～４のアルキレン基である。Ａ1とＡ2とは同じでも異なってもよい。）で示されるものが使用できる。
  ポリエーテルジアミンは、ポリエーテルジオールの水酸基を公知の方法によりアミノ基に変えることにより得ることができ、例えば、ポリエーテルジオールの水酸基をシアノアルキル化して得られる末端を還元してアミノ基としたものが使用できる。例えばポリエーテルジオールとアクリロニトリルとを反応させ、得られるシアノエチル化物を水素添加することにより製造することができる。 The polyether diamine has the general formula: H 2 N—A 2 — (OA 1) m —O—E 1 —O— (A 1 O) m′-A 2 —NH 2 (wherein the symbols E 1, A 1, m and m ′ are A2 is a C2-4 alkylene group, and A1 and A2 may be the same or different.
The polyether diamine can be obtained by changing the hydroxyl group of the polyether diol to an amino group by a known method, for example, by reducing the terminal obtained by cyanoalkylating the hydroxyl group of the polyether diol to an amino group Can be used. For example, it can be produced by reacting polyether diol with acrylonitrile and hydrogenating the resulting cyanoethylated product.
　変性物としては、例えば、ポリエーテルジオールまたはポリエーテルジアミンのアミノカルボン酸変性物（末端アミノ基）、同イソシアネート変性物（末端イソシアネート基）および同エポキシ変性物（末端エポキシ基）が挙げられる。
  アミノカルボン酸変性物は、ポリエーテルジオールまたはポリエーテルジアミンと、アミノカルボン酸またはラクタムとを反応させることにより得ることができる。 Examples of the modified product include polyether diol or polyether diamine aminocarboxylic acid modified product (terminal amino group), the same isocyanate modified product (terminal isocyanate group) and the same epoxy modified product (terminal epoxy group).
The aminocarboxylic acid-modified product can be obtained by reacting polyether diol or polyether diamine with aminocarboxylic acid or lactam.
　ポリエーテルとポリオレフィンとのブロックポリマーを構成するポリオレフィンとしては、カルボニル基（好ましくは、カルボキシル基、以下同じ。）をポリマーの両末端に有するポリオレフィン、水酸基をポリマーの両末端に有するポリオレフィン、およびアミノ基をポリマーの両末端に有するポリオレフィンおよびイソシアネート基をポリマーの両末端に有するポリオレフィン等のいずれかが使用できる。
　さらに、カルボニル基をポリマーの片末端に有するポリオレフィン、水酸基をポリマーの片末端に有するポリオレフィン、アミノ基をポリマーの片末端に有するポリオレフィン、およびイソシアネート基をポリマーの片末端に有するポリオレフィン等のいずれかを使用できる。
　これらのうち、変性のし易さからカルボニル基を有するポリオレフィンおよびカルボニル基をポリマーの片末端に有するポリオレフィンが好ましい。 Polyolefins constituting the block polymer of polyether and polyolefin include polyolefins having carbonyl groups (preferably carboxyl groups, the same shall apply hereinafter) at both ends of the polymer, polyolefins having hydroxyl groups at both ends of the polymer, and amino groups. Can be used, such as polyolefin having both at both ends of the polymer and polyolefin having isocyanate groups at both ends of the polymer.
Furthermore, a polyolefin having a carbonyl group at one end of the polymer, a polyolefin having a hydroxyl group at one end of the polymer, a polyolefin having an amino group at one end of the polymer, a polyolefin having an isocyanate group at one end of the polymer, etc. Can be used.
Among these, a polyolefin having a carbonyl group and a polyolefin having a carbonyl group at one end of the polymer are preferable because of easy modification.
　次に、ポリエーテルエステルアミドについて説明する。ポリエーテルエステルアミドは、たとえば、両端にカルボキシル基を有するポリアミドと、ポリエーテルジオールとを共重合させたものである。
　ポリアミドとしては、ラクタムの開環重合体や、アミノカルボン酸の自己重合体等のいずれか１種以上があげられる。 Next, polyether ester amide will be described. The polyether ester amide is, for example, a copolymer of polyamide having carboxyl groups at both ends and polyether diol.
Examples of the polyamide include one or more of a ring-opening polymer of lactam and a self-polymer of aminocarboxylic acid.
　本発明の樹脂組成物は、成分（Ａ）と成分（Ｂ）と成分（Ｃ）と成分（Ｄ）との合計１００重量部に対し、成分（Ｅ）を合計で７～１５重量部含有する。７重量部以上とすることで、成形品の表面抵抗値を低いものとすることができる。一方で、１５重量部以下とすることで、耐熱性を確保することができる。なかでも、耐熱性、耐衝撃性、静電気放電防止性能のバランスの観点から、成分（Ａ）と成分（Ｂ）と成分（Ｃ）と成分（Ｄ）との合計１００重量部に対し、成分（Ｅ）を合計で１０重量部以上含有することが好ましい。
　一般に、樹脂組成物中の帯電防止剤の添加量を多くすると、表面抵抗値を低くすることはできるものの、耐熱性が劣るものとなる。一方で、帯電防止剤の添加量を低くすると、表面抵抗値が高くなってしまう。これに対し、本発明では、成分（Ｄ）の含有量を所定量とするとともに、特定構造の成分（Ｅ）を使用することで、成分（Ｅ）の含有量を成分（Ａ）と成分（Ｂ）と成分（Ｃ）と成分（Ｄ）との合計１００重量部に対し、１５重量部以下と低い値としても、低い表面抵抗値とすることができ、かつ、耐熱性に優れたものとすることができる。 The resin composition of the present invention contains 7 to 15 parts by weight of component (E) in total with respect to 100 parts by weight of component (A), component (B), component (C) and component (D). . By setting it as 7 weight part or more, the surface resistance value of a molded article can be made low. On the other hand, heat resistance can be ensured by setting it as 15 weight part or less. Among them, from the viewpoint of balance of heat resistance, impact resistance, and electrostatic discharge prevention performance, the component (A), the component (B), the component (C), and the component (D) are added to the component ( It is preferable to contain 10 parts by weight or more of E) in total.
In general, when the amount of the antistatic agent added in the resin composition is increased, the surface resistance value can be lowered, but the heat resistance is inferior. On the other hand, when the addition amount of the antistatic agent is lowered, the surface resistance value is increased. In contrast, in the present invention, the content of the component (D) is set to a predetermined amount, and the component (E) having a specific structure is used to reduce the content of the component (E) to the component (A) and the component ( B) With respect to a total of 100 parts by weight of component (C) and component (D), even if the value is as low as 15 parts by weight or less, the surface resistance value can be reduced and the heat resistance is excellent. can do.
　本発明の樹脂組成物は、上記の成分の他に、その物性を損なわない限りにおいて、その目的に応じて、他の添加剤、例えば顔料、染料、充填剤（ガラス繊維、マイカ、シリカなど）、酸化劣化防止剤、耐候剤、滑剤、離型剤等を含んでもよい。
　ただし、本発明の樹脂組成物は、導電性カーボンブラック等の導電性の充填剤を含まないことが好ましい。導電性の充填剤を含まないことで、成形加工性を確保することができ、さらには、材料の着色が制限されてしまうことを防止できる。カーボン落ちによる汚れ防止にもなる。
　また、本発明の樹脂組成物を製造するための方法に特に制限はないが、溶融混合法が望ましい。 In addition to the above components, the resin composition of the present invention may have other additives such as pigments, dyes, fillers (glass fibers, mica, silica, etc.) depending on the purpose as long as the physical properties are not impaired. Further, an antioxidant may be included, a weathering agent, a lubricant, a release agent, and the like.
However, the resin composition of the present invention preferably does not contain a conductive filler such as conductive carbon black. By not containing a conductive filler, molding processability can be ensured, and further, coloring of the material can be prevented from being limited. It also prevents dirt from falling off the carbon.
The method for producing the resin composition of the present invention is not particularly limited, but a melt mixing method is desirable.
　以上のような当該半導体集積回路装置包装トレイ用樹脂組成物から得られる射出成形品は、以下の要件を満たす。
（ａ）ＩＳＯ７５に準拠して測定される荷重たわみ温度（荷重1.8ＭＰａ）が１６０℃以上（ただし、ＩＳＯ１７９に準拠した方法により４ｍｍ（厚さ）×１０ｍｍ（幅）×８０ｍｍ（長さ）の試験片を用いて測定）
（ｂ）ＩＳＯ１７９に準拠して測定されるシャルピー衝撃強度の値が５ｋＪ／ｍ２以上（ただし、ＩＳＯ１７９に準拠した方法により４ｍｍ（厚さ）×１０ｍｍ（幅）×８０ｍｍ（長さ）の試験片を用いて測定）
（ｃ）表面固有抵抗値が１０１０Ω／□未満　
　したがって、耐熱性、耐衝撃性、静電気放電防止性能のバランスに優れたトレイを製造できる半導体集積回路装置包装トレイ用樹脂組成物が提供できる。
　なお、成形品は、以下のようにして製造される。
　樹脂組成物を２軸押出機を用いて、押出温度３００℃、回転数１５０ｒｐｍで溶融混練し、ペレットを得る。次に、このペレットを用いて、設定温度３００℃、金型温度１２０℃の条件にて射出成形して、所定の厚みの試験片を製造する。その後、上記（ａ）～（ｃ）の物性の計測を行なう。ただし、（ａ）の計測を行なう場合には、試験片を１５５℃で５時間加熱し、恒温恒湿室（２３℃５０％ＨＲ）に２４時間放置した後、（ａ）の計測を行なう。
　以上のような樹脂組成物を使用し、押出成形、射出成形等することで、所望の性能を有する半導体集積回路装置包装トレイを得ることができる。
　なお、（ａ）の荷重たわみ温度の上限値は特に限定されないが、たとえば、２００℃である。また、（ｂ）のシャルピー衝撃強度の上限値は、特に限定されないが、１０ｋＪ／ｍ２である。さらには、（ｃ）の表面固有抵抗値の下限値は特に限定されないが、たとえば、１×１０４Ω/□である。 The injection molded product obtained from the resin composition for a semiconductor integrated circuit device packaging tray as described above satisfies the following requirements.
(A) Deflection temperature (load 1.8 MPa) measured according to ISO75 is 160 ° C. or higher (however, a test of 4 mm (thickness) × 10 mm (width) × 80 mm (length) by a method according to ISO179) Measurement using a piece)
(B) A test piece having a Charpy impact strength value measured in accordance with ISO 179 of 5 kJ / m 2 or more (however, a test piece of 4 mm (thickness) × 10 mm (width) × 80 mm (length) by a method in accordance with ISO 179) Measure using
(C) Surface resistivity is less than 10 10 Ω / □
Therefore, it is possible to provide a resin composition for a semiconductor integrated circuit device packaging tray capable of producing a tray excellent in balance of heat resistance, impact resistance, and electrostatic discharge prevention performance.
In addition, a molded article is manufactured as follows.
The resin composition is melt-kneaded using a twin screw extruder at an extrusion temperature of 300 ° C. and a rotation speed of 150 rpm to obtain pellets. Next, a test piece having a predetermined thickness is manufactured by injection molding using the pellets under conditions of a set temperature of 300 ° C. and a mold temperature of 120 ° C. Thereafter, the physical properties (a) to (c) are measured. However, when the measurement of (a) is performed, the test piece is heated at 155 ° C. for 5 hours and left in a constant temperature and humidity chamber (23 ° C., 50% HR) for 24 hours, and then the measurement of (a) is performed.
A semiconductor integrated circuit device packaging tray having desired performance can be obtained by using the resin composition as described above and performing extrusion molding, injection molding, or the like.
The upper limit value of the deflection temperature under load (a) is not particularly limited, but is 200 ° C., for example. Moreover, the upper limit value of the Charpy impact strength of (b) is not particularly limited, but is 10 kJ / m 2 . Furthermore, the lower limit value of the surface specific resistance value of (c) is not particularly limited, but is, for example, 1 × 10 4 Ω / □.
　次に、本発明の実施例について説明する。
　以下の実施例および比較例では、次の化合物を使用した。
（Ａ）ポリフェニレンエーテル樹脂
ＰＰＥ－Ａ：固有粘度（クロロホルム中、２５℃で測定）０．３５ｄｌ／ｇのポリ（２，６－ジメチル－１，４－フェニレンエーテル）、商品名：ＬＸＲ０３５、Bluestar New chemical materials Co. Ltd, 製
ＰＰＥ－Ｂ：固有粘度（クロロホルム中、２５℃で測定）０．４ｄｌ／ｇのポリ（２，６－ジメチル－１，４－フェニレンエーテル）、商品名：ＬＸＲ０４０、Bluestar New chemicals materials Co. Ltd, 製
ＰＰＥ－Ｃ：固有粘度（クロロホルム中、２５℃で測定）０．４５ｄｌ／ｇのポリ（２，６－ジメチル－１，４－フェニレンエーテル）、商品名：ＬＸＲ０４５、Bluestar New chemicals materials Co. Ltd, 製
　なお、表１，２において、ＰＰＥ粘度は加重平均を示し、各ＰＰＥの粘度にＰＰＥ合計に対する各ＰＰＥの重量比率をかけたものを、加算した値である。 Next, examples of the present invention will be described.
In the following Examples and Comparative Examples, the following compounds were used.
(A) Polyphenylene ether resin PPE-A: poly (2,6-dimethyl-1,4-phenylene ether) with an intrinsic viscosity (measured in chloroform at 25 ° C.) of 0.35 dl / g, trade names: LXR035, Bluestar New PPE-B manufactured by chemical materials Co. Ltd, poly (2,6-dimethyl-1,4-phenylene ether) with an intrinsic viscosity (measured in chloroform at 25 ° C.) of 0.4 dl / g, trade names: LXR040, Bluestar New chemicals materials Co. Ltd, PPE-C: Intrinsic viscosity (measured in chloroform at 25 ° C.) 0.45 dl / g poly (2,6-dimethyl-1,4-phenylene ether), trade name: LXR045, Bluestar New chemicals materials Co., Ltd. In Tables 1 and 2, PPE viscosity indicates a weighted average, and the viscosity of each PPE is the weight ratio of each PPE to the total PPE. Was the thing, is added value.
（Ｂ）ポリスチレン樹脂
ＨＩＰＳ：ハイインパクトポリスチレン樹脂、商品名：ＨＴ４７８、ＰＳジャパン株式会社製 (B) Polystyrene resin HIPS: high impact polystyrene resin, trade name: HT478, manufactured by PS Japan Ltd.
（Ｃ）スチレン系エラストマー
ＳＥＢＳ－Ａ：スチレン・エチレン・ブチレン・スチレンブロックコポリマー、商品名：タフテックＨ１０４１Ｇ、旭化成ケミカルズ株式会社製
ＳＥＢＳ－Ｂ：無水マレイン酸変性スチレン・エチレン・ブチレン・スチレンブロックコポリマー、商品名：タフテックＭ１９１１、旭化成ケミカルズ株式会社製 (C) Styrenic elastomer SEBS-A: styrene / ethylene / butylene / styrene block copolymer, trade name: Tuftec H1041G, SEBS-B manufactured by Asahi Kasei Chemicals Corporation: maleic anhydride modified styrene / ethylene / butylene / styrene block copolymer, product Name: Tuftec M1911, manufactured by Asahi Kasei Chemicals Corporation
（Ｄ）タルク
商品名：Ｐ－タルク、平均粒径９μｍ、竹原化学工業株式会社製 (D) Product name of talc: P-talc, average particle size 9μm, manufactured by Takehara Chemical Industry Co., Ltd.
（Ｅ）ポリエーテル系ブロックポリマー
Ｅ－１：商品名：ペレクトロンＨＳ、三洋化成工業株式会社製、ポリアミドの共重合体（抵抗値4×106Ω/□）
Ｅ－２：商品名：ペレクトロンＭＰ、三洋化成工業株式会社製、ポリアミドの共重合体（抵抗値8×105Ω/□）
　なお、Ｅ－１、Ｅ－２はいずれも、ポリエーテルとポリオレフィンとのブロックポリマー、および、ポリエーテルエステルアミドのうちの少なくともいずれか一方を含む。
　また、抵抗値は、以下のように測定した。
　成分（Ｅ）を220℃でプレス成型し、23℃50%RHで24時間調湿後、表面抵抗計(SIMCO JAPAN株式会社製 ST-4)にて測定した。 (E) Polyether block polymer E-1: Trade name: Peletron HS, manufactured by Sanyo Chemical Industries, Ltd., polyamide copolymer (resistance value 4 × 10 6 Ω / □)
E-2: Trade name: Peletron MP, manufactured by Sanyo Chemical Industries, Ltd., polyamide copolymer (resistance value 8 × 10 5 Ω / □)
Each of E-1 and E-2 includes at least one of a block polymer of polyether and polyolefin and polyether ester amide.
Moreover, the resistance value was measured as follows.
The component (E) was press-molded at 220 ° C., conditioned at 23 ° C. and 50% RH for 24 hours, and then measured with a surface resistance meter (ST-4, manufactured by SIMCO JAPAN).
　また、比較例において、帯電防止剤として、イルガスタットP18（ポリエーテルエステルアミド組成物）、BASFジャパン株式会社製（抵抗値6×107Ω/□）、エンティラ（エチレン不飽和カルボン酸共重合体）、三井・デュポンポリケミカル株式会社製（抵抗値7×107Ω/□）を使用した。
　なお、表１，２において、成分（Ｂ）、（Ｃ）、（Ｄ）は、成分（Ａ）１００重量部に対する割合（重量部）を示し、成分（Ｅ）は、成分（Ａ）～（Ｄ）の合計を１００重量部とした場合の割合（重量部）を示している。 In the comparative example, as antistatic agent, Irgastat P18 (polyetheresteramide composition), manufactured by BASF Japan Ltd. (resistance value 6 × 10 7 Ω / □), entilla (ethylene unsaturated carboxylic acid copolymer) ), Mitsui DuPont Polychemical Co., Ltd. (resistance value 7 × 10 7 Ω / □) was used.
In Tables 1 and 2, components (B), (C), and (D) indicate ratios (parts by weight) to 100 parts by weight of component (A), and component (E) includes components (A) to (A). The ratio (part by weight) when the total of D) is 100 parts by weight is shown.
（実施例１）
　表１に示す配合のペレット（樹脂組成物）を作成した。
　具体的には、ＰＰＥ－Ａ（成分（Ａ））３０．０重量部、ＰＰＥ－Ｃ（成分（Ａ））７０．０重量部、ＨＩＰＳ（成分（Ｂ））１８．０重量部、ＳＥＢＳ－Ｂ（成分（Ｃ））９．０重量部、Ｅ－２（成分（Ｅ））１０重量部、タルク（成分（Ｄ））５５．０重量部を、２軸押出機を用いて、押出温度３００℃、回転数１５０ｒｐｍで溶融混練し、ペレットを得た。次に、このペレットを用いて、設定温度３００℃、金型温度１２０℃の条件にて射出成形した。得られた成形品（試験片）について、以下の試験を実施した。試験結果を表１に示す。また、同様にしてトレイ成形物が得られた。 (Example 1)
Pellets (resin composition) having the composition shown in Table 1 were prepared.
Specifically, PPE-A (component (A)) 30.0 parts by weight, PPE-C (component (A)) 70.0 parts by weight, HIPS (component (B)) 18.0 parts by weight, SEBS- B (component (C)) 9.0 parts by weight, E-2 (component (E)) 10 parts by weight, talc (component (D)) 55.0 parts by weight using a twin screw extruder, extrusion temperature Melt kneading was performed at 300 ° C. and a rotation speed of 150 rpm to obtain pellets. Next, this pellet was used for injection molding under the conditions of a preset temperature of 300 ° C. and a mold temperature of 120 ° C. The following test was implemented about the obtained molded article (test piece). The test results are shown in Table 1. Similarly, a tray molded product was obtained.
（１）シャルピー衝撃強さ
　ＩＳＯ１７９に準じて、下記条件でシャルピー衝撃強さ（Ｅｄｇｅｗｉｓｅ Ｉｍｐａｃｔ、ノッチ付き）を測定した。測定値の単位は、ｋＪ／ｍ２である。
試験片タイプ ； ４ｍｍ（厚さ）×１０ｍｍ（幅）×８０ｍｍ（長さ）
ノッチタイプ ； Ｔｙｐｅ Ａ
荷重 ； ２Ｊ
温度 ； ２５℃ (1) Charpy impact strength Charpy impact strength (Edgewise Impact, with notch) was measured according to ISO179 under the following conditions. Units of measurement are kJ / m 2.
Test piece type: 4 mm (thickness) x 10 mm (width) x 80 mm (length)
Notch type; Type A
Load; 2J
Temperature: 25 ° C
（２）荷重たわみ温度（ＨＤＴ）（℃）
  試験片を１５５℃で５時間加熱し、恒温恒湿室（２３℃５０％ＨＲ）に２４時間放置した後、ＩＳＯ７５に準拠し、荷重たわみ温度（荷重1.8ＭＰａ）を測定した。
試験片：４ｍｍ（厚さ）×１０ｍｍ（幅）×８０ｍｍ（長さ）
荷重：１．８ＭＰａ、支点間距離６４ｍｍ、昇温速度１２０℃／ｈｒ
規定たわみ量：０．３２ｍｍたわみ (2) Deflection temperature under load (HDT) (° C)
The test piece was heated at 155 ° C. for 5 hours and left in a constant temperature and humidity chamber (23 ° C., 50% HR) for 24 hours, and then the deflection temperature under load (load 1.8 MPa) was measured according to ISO75.
Test piece: 4 mm (thickness) x 10 mm (width) x 80 mm (length)
Load: 1.8 MPa, distance between fulcrums of 64 mm, heating rate of 120 ° C./hr
Specified deflection amount: 0.32mm deflection
（３）表面抵抗値（Ω／□）
　ＪＩＳ　Ｋ　６９１１に準拠した表面抵抗計（三菱化学株式会社製、高抵抗率計　商品名ハイレスターＵＰ（ＭＣＰ－ＨＴ４５０）のリング電極方式を用い、ＪＩＳ　Ｋ　６９１１に準拠し、測定した。試験片は８０ｍｍ×１６０ｍｍ×２ｍｍの平板である。 (3) Surface resistance (Ω / □)
A surface resistance meter in accordance with JIS K 6911 (manufactured by Mitsubishi Chemical Co., Ltd., high resistivity meter, trade name Hirester UP (MCP-HT450) was used and measured in accordance with JIS K 6911. It is a flat plate of 80 mm × 160 mm × 2 mm.
（４）外観
　トレイ成形物の外観を目視で観察した。
◎：フローマークが一見して目立たない
○：フローマークは成型物の一部に一見して認められる
△：フローマークが成型物全体にあるが、実用に問題はない (4) Appearance The appearance of the tray molded product was visually observed.
◎: The flow mark is inconspicuous ○: The flow mark is recognized at a part of the molded product Δ: The flow mark is present in the entire molded product, but there is no problem in practical use
（実施例２～１３）
　表１に示す配合で、実施例１と同様に、ペレットを得た。そして、実施例１と同様にペレットを射出成形し、試験片を作成した。また、同様にしてトレイ成形物が得られた。
　さらに、実施例１と同様に、試験を実施した。 (Examples 2 to 13)
With the formulation shown in Table 1, pellets were obtained in the same manner as in Example 1. And the pellet was injection-molded similarly to Example 1, and the test piece was created. Similarly, a tray molded product was obtained.
Further, the test was performed in the same manner as in Example 1.
（比較例１～１０）
　表２に示す配合で、実施例１と同様に、ペレットを得た。そして、実施例１と同様にペレットを射出成形し、試験片を作成した。
　また、実施例１と同様に、試験を実施した。 (Comparative Examples 1 to 10)
With the formulation shown in Table 2, pellets were obtained in the same manner as in Example 1. And the pellet was injection-molded similarly to Example 1, and the test piece was created.
In addition, the test was performed in the same manner as in Example 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　実施例１～１３では、シャルピー衝撃強度が５ｋＪ／ｍ２以上、荷重たわみ温度が１６０℃以上、表面抵抗値が１×１０10Ω／□未満となり、耐衝撃性、耐熱性、表面抵抗値に優れたものとなった。また、酸変性スチレン系エラストマーを使用した場合には、外観が特に良好となることがわかった。
　これに対し、比較例１では、成分（Ｅ）含有量が少なかったため、表面抵抗値が高くなってしまった。比較例２では、成分（Ｅ）の含有量が多すぎたため、耐熱性が低くなってしまった。比較例３～６では、成分（Ｅ）とは異なる帯電防止剤を使用しているため、表面抵抗値が高いものとなってしまった。さらに、比較例７では、成分（Ａ）の粘度が低すぎたため、耐衝撃性に劣るものとなった。また、比較例８では、成分（Ｃ）の含有量が少なすぎたため、耐衝撃性に劣るものとなった。比較例９では、成分（Ｃ）の含有量が多すぎたため、耐熱性に劣るものとなった。比較例１０では、成分（Ｂ）が多すぎたため、耐熱性に劣るものとなった。
　また、実施例１～１３は、特許文献１に開示されたものよりも耐衝撃性、耐熱性、表面抵抗値のバランスに優れたものとなった。 In Examples 1 to 13, the Charpy impact strength is 5 kJ / m 2 or more, the deflection temperature under load is 160 ° C. or more, the surface resistance value is less than 1 × 10 10 Ω / □, and the impact resistance, heat resistance, and surface resistance value are improved. It was excellent. Further, it was found that the appearance is particularly good when an acid-modified styrene elastomer is used.
On the other hand, in Comparative Example 1, since the content of the component (E) was small, the surface resistance value was high. In Comparative Example 2, the heat resistance was low because the content of component (E) was too large. In Comparative Examples 3 to 6, since an antistatic agent different from the component (E) was used, the surface resistance value was high. Furthermore, in Comparative Example 7, since the viscosity of the component (A) was too low, the impact resistance was poor. In Comparative Example 8, the content of the component (C) was too small, so that the impact resistance was poor. In comparative example 9, since there was too much content of a component (C), it became inferior to heat resistance. In comparative example 10, since there were too many components (B), it became inferior to heat resistance.
In addition, Examples 1 to 13 were superior in balance of impact resistance, heat resistance, and surface resistance value to those disclosed in Patent Document 1.

Claims (6)

  1. （Ａ）ポリフェニレンエーテル樹脂
    （Ｂ）ポリスチレン樹脂（成分（Ｃ）を除く）を成分（Ａ）１００重量部に対して、０～２０重量部
    （Ｃ）スチレン系エラストマーを成分（Ａ）１００重量部に対して、３～１２重量部
    （Ｄ）タルクを成分（Ａ）１００重量部に対して、３５～７０重量部
    を含むとともに、
    （Ｅ）ポリエーテル系ブロックポリマーであり、ポリエーテルとポリオレフィンとのブロックポリマー、および、ポリエーテルエステルアミドのうちの少なくとも何れか一方を含み、
    　成分（Ｅ）の含有量が成分（Ａ）と成分（Ｂ）と成分（Ｃ）と成分（Ｄ）との合計１００重量部に対し、７～１５重量部である樹脂組成物であり、
    　当該樹脂組成物から得られる成形品が以下の要件を満たす半導体集積回路装置包装トレイ用樹脂組成物。
    （ａ）ＩＳＯ７５に準拠して測定される荷重たわみ温度（荷重1.8ＭＰａ）が１６０℃以上
    （ｂ）ＩＳＯ１７９に準拠して測定されるシャルピー衝撃強度の値が５ｋＪ／ｍ２以上
    （ｃ）表面固有抵抗値が１０１０Ω／□未満     (A) Polyphenylene ether resin (B) Polystyrene resin (excluding component (C)) with respect to 100 parts by weight of component (A) 0 to 20 parts by weight (C) 100 parts by weight of component (A) styrene elastomer 3 to 12 parts by weight (D) talc with respect to 100 parts by weight of component (A) and 35 to 70 parts by weight,
    (E) a polyether block polymer, including at least one of a block polymer of polyether and polyolefin, and a polyether ester amide;
    A resin composition in which the content of component (E) is 7 to 15 parts by weight with respect to 100 parts by weight in total of component (A), component (B), component (C) and component (D),
    A resin composition for a semiconductor integrated circuit device packaging tray, in which a molded product obtained from the resin composition satisfies the following requirements.
    (A) Deflection temperature (load 1.8 MPa) measured according to ISO75 is 160 ° C. or higher (b) Charpy impact strength value measured according to ISO179 is 5 kJ / m 2 or more (c) Surface specific Resistance value is less than 10 10 Ω / □
  2. 　請求項１に記載の半導体集積回路装置包装トレイ用樹脂組成物において、
    　前記成分（Ｂ）の含有量が、成分（Ａ）１００重量部に対し、１０重量部以上、２０重量部以下である半導体集積回路装置包装トレイ用樹脂組成物。     In the resin composition for a semiconductor integrated circuit device packaging tray according to claim 1,
    The resin composition for a semiconductor integrated circuit device packaging tray, wherein the content of the component (B) is 10 parts by weight or more and 20 parts by weight or less with respect to 100 parts by weight of the component (A).
  3. 　請求項１または２に記載の半導体集積回路装置包装トレイ用樹脂組成物において、
    　前記成分（Ｂ）がハイインパクトポリスチレン（ＨＩＰＳ：スチレン－ブタジエン共重合体）を含む半導体集積回路装置包装トレイ用樹脂組成物。     In the resin composition for semiconductor integrated circuit device packaging trays according to claim 1 or 2,
    A resin composition for a semiconductor integrated circuit device packaging tray, wherein the component (B) contains high impact polystyrene (HIPS: styrene-butadiene copolymer).
  4. 　請求項１乃至３のいずれかに記載の半導体集積回路装置包装トレイ用樹脂組成物において、
    　前記成分（Ｃ）は酸変性スチレン系エラストマーを含む半導体集積回路装置包装トレイ用樹脂組成物。     In the resin composition for semiconductor integrated circuit device packaging trays according to any one of claims 1 to 3,
    The component (C) is a resin composition for a semiconductor integrated circuit device packaging tray containing an acid-modified styrene elastomer.
  5. 　請求項１に記載の半導体集積回路装置包装トレイ用樹脂組成物において、
    　前記成分（Ａ）のポリフェニレンエーテル樹脂の固有粘度が加重平均で０．３６～０．４６ｄｌ／ｇであり、
    　前記成分（Ｅ）の抵抗値が、１×１０7Ω/□未満である半導体集積回路装置包装トレイ用樹脂組成物。     In the resin composition for a semiconductor integrated circuit device packaging tray according to claim 1,
    The intrinsic viscosity of the polyphenylene ether resin of the component (A) is 0.36 to 0.46 dl / g in terms of weighted average,
    A resin composition for a semiconductor integrated circuit device packaging tray, wherein the resistance value of the component (E) is less than 1 × 10 7 Ω / □.
  6. 　請求項１乃至５のいずれかに記載の半導体集積回路装置包装トレイ用樹脂組成物により構成された半導体集積回路装置包装トレイ。 A semiconductor integrated circuit device packaging tray comprising the resin composition for a semiconductor integrated circuit device packaging tray according to any one of claims 1 to 5.
PCT/JP2012/008165 2012-12-20 2012-12-20 Resin composition for semiconductor integrated circuit device packaging tray and semiconductor integrated circuit device packaging tray WO2014097360A1 (en)

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JPH06240131A (en) * 1993-02-16 1994-08-30 Mitsubishi Gas Chem Co Inc Electrically conductive polyphenylene ethereal resin composition
JPH08188710A (en) * 1995-01-10 1996-07-23 Asahi Chem Ind Co Ltd Electroconductive resin composition having good extruding property
JPH10316847A (en) * 1997-05-19 1998-12-02 Asahi Chem Ind Co Ltd Resin composition and molded product for heat-resistant ic member
JP2001192517A (en) * 2000-01-12 2001-07-17 Denki Kagaku Kogyo Kk Resin composition and container for electronic part
JP2011006627A (en) * 2009-06-29 2011-01-13 Lion Corp Conductive polyphenylene ether resin composition for forming electric and electronic component packaging material
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JPH03188158A (en) * 1989-10-20 1991-08-16 General Electric Co <Ge> Antistatic polyphenylene ether resin composition and method for imparting antistatic property
JPH06240131A (en) * 1993-02-16 1994-08-30 Mitsubishi Gas Chem Co Inc Electrically conductive polyphenylene ethereal resin composition
JPH08188710A (en) * 1995-01-10 1996-07-23 Asahi Chem Ind Co Ltd Electroconductive resin composition having good extruding property
JPH10316847A (en) * 1997-05-19 1998-12-02 Asahi Chem Ind Co Ltd Resin composition and molded product for heat-resistant ic member
JP2001192517A (en) * 2000-01-12 2001-07-17 Denki Kagaku Kogyo Kk Resin composition and container for electronic part
JP2011006627A (en) * 2009-06-29 2011-01-13 Lion Corp Conductive polyphenylene ether resin composition for forming electric and electronic component packaging material
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JP2013014702A (en) * 2011-07-05 2013-01-24 Riken Technos Corp Thermoplastic resin composition

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CN109852032A (en) * 2019-02-13 2019-06-07 湖南恒屹新材料有限公司 A kind of polyphenylene oxide resin based composites and its preparation method and application

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