WO2013150979A1 - Composition de résine - Google Patents

Composition de résine Download PDF

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Publication number
WO2013150979A1
WO2013150979A1 PCT/JP2013/059591 JP2013059591W WO2013150979A1 WO 2013150979 A1 WO2013150979 A1 WO 2013150979A1 JP 2013059591 W JP2013059591 W JP 2013059591W WO 2013150979 A1 WO2013150979 A1 WO 2013150979A1
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Prior art keywords
component
resin composition
mass
parts
manufactured
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PCT/JP2013/059591
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English (en)
Japanese (ja)
Inventor
大夢 佐藤
勝由 江幡
雅則 二階堂
鈴木　勤
三村　博
Original Assignee
ライオン株式会社
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Application filed by ライオン株式会社 filed Critical ライオン株式会社
Priority to KR1020147026025A priority Critical patent/KR102000809B1/ko
Priority to CN201380018465.3A priority patent/CN104245832B/zh
Priority to MYPI2014702847A priority patent/MY184861A/en
Publication of WO2013150979A1 publication Critical patent/WO2013150979A1/fr

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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
    • C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
    • 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
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • 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
    • 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
    • C08L23/06—Polyethene
    • 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
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/40—Polymerisation processes
    • C08G2261/41—Organometallic coupling reactions
    • C08G2261/418—Ring opening metathesis polymerisation [ROMP]
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/70—Post-treatment
    • C08G2261/72—Derivatisation
    • C08G2261/724—Hydrogenation
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a resin composition.
  • the present invention claims priority based on Japanese Patent Application No. 2012-085075 filed in Japan on April 4, 2012, the contents of which are incorporated herein by reference.
  • a semiconductor storage and conveyance container made of a resin molded body is used to convey or store a wafer or the like.
  • the performance required for semiconductor storage and transport containers includes mechanical strength against bending, impact, heat resistance, and antistatic properties (ie, conductivity) to prevent dust or dust adhesion or circuit breakdown. It is mentioned that it is excellent.
  • a resin composition for providing such a semiconductor storage and conveyance container for example, a resin composition containing a cyclic olefin copolymer, an olefin-based resin, and a conductive filler has been proposed (see Patent Document 1).
  • the glass transition temperature obtained by polymerizing a cyclic olefin polymer having a specific glass transition temperature and two or more monomers selected from the group consisting of olefin, diene and aromatic vinyl hydrocarbon is 0 ° C. or less.
  • a resin composition obtained by melt-kneading a soft copolymer, a radical initiator, and a polyfunctional compound having two or more radical polymerizable functional groups in the molecule has been proposed (see Patent Document 2). ).
  • one embodiment of the resin composition of the present invention comprises a cyclic olefin homopolymer (A) having a glass transition temperature of 101 to 160 ° C., a fibrous conductive filler (B), an olefin elastomer and a styrene elastomer. And containing at least one elastomer (C) selected from the group consisting of 5 to 25 parts by mass with respect to 100 parts by mass of the cyclic olefin homopolymer (A). It is characterized by.
  • the resin composition of the present invention preferably further contains polyethylene (D) having a viscosity average molecular weight of 1,000,000 or more. Moreover, it is preferable that the resin composition of this invention further contains a particulate conductive filler (E).
  • the particulate conductive filler (E) is preferably carbon black having an n-dibutyl phthalate oil absorption of 180 mL / 100 g or more.
  • the resin composition of the present invention is selected from the group consisting of a cyclic olefin homopolymer (A) having a glass transition temperature of 101 to 160 ° C., a fibrous conductive filler (B), an olefin elastomer and a styrene elastomer. Containing at least one elastomer (C).
  • a cyclic olefin homopolymer A having a glass transition temperature of 101 to 160 ° C.
  • B fibrous conductive filler
  • an olefin elastomer and a styrene elastomer Containing at least one elastomer (C).
  • these components are also referred to as component (A), component (B), and component (C), respectively.
  • the component (A) is used as a base resin for the resin composition.
  • the resin composition contains the component (A)
  • it is excellent in low outgassing in addition to heat resistance.
  • the component (A) has a low water absorption compared to other types of thermoplastic resins, when the resin composition containing the component (A) is formed into a molded body, it is possible to prevent moisture from adhering to a wafer or the like. .
  • Cyclic olefin homopolymer means a polymer (homopolymer) obtained by homopolymerizing the cyclic olefin using a cyclic olefin as a monomer, and the main chain of the polymer has a cyclic hydrocarbon structure composed of carbon-carbon bonds. It is a polymer compound.
  • the cyclic olefin refers to a cyclic hydrocarbon having at least one olefin (double bond) represented by norbornene and tetracyclododecene.
  • polycyclic olefins represented by norbornene and tetracyclododecene are preferable.
  • Examples of the component (A) include a ring-opening polymer of a monomer having a norbornene ring or a hydrogenated product thereof disclosed in JP-A-1-168724 and JP-A-1-168725.
  • the monomer having a norbornene ring is a bicyclic olefin norbornene that is an adduct of ethylene and cyclopentadiene, or a tetracyclic olefin tetracyclododecene or cyclopentadiene that is obtained by adding cyclopentadiene to norbornene.
  • a tricyclic diene tricyclodecadiene also called dicyclopentadiene
  • a tricyclic olefin tricyclodecene and cyclopentadiene trimer in which a part of the unsaturated bond of dicyclopentadiene is saturated by hydrogenation.
  • Pentacyclopentadecene, a pentacyclic diene, pentacyclopentadecene, a pentacyclic olefin in which part of the unsaturated bond of pentacyclopentadedecadiene is saturated by hydrogenation also known as 2,3-dihydrodicyclopentadiene
  • substitutions thereof are exemplified. .
  • glass transition temperature (Tg) indicates a value measured by a method based on JIS K7121.
  • the Tg of the component (A) is 101 to 160 ° C., preferably 101 to 150 ° C., more preferably 101 to 140 ° C., particularly preferably 102 to 140 ° C., and most preferably 105 to 140 ° C. If Tg of (A) component is 101 degreeC or more, the generation amount of outgas will be easy to reduce. In addition, the heat resistance is further increased. If Tg is 160 ° C. or lower, the amount of outgas generated is likely to be reduced.
  • the component (A) in the resin composition, as the component (A), one type may be used alone, or two or more types may be used in combination.
  • the component (A) is preferably a ring-opening polymer of a monomer having a Tg of 101 to 160 ° C. and having a norbornene ring or a hydrogenated product thereof, because the effects of the present invention are more excellent.
  • a hydrogenated product of a ring-opening polymer is particularly preferable.
  • the number average molecular weight of the component (A) is preferably 3,000 to 500,000, and more preferably 8,000 to 200,000.
  • the aspect ratio of the component (B) is preferably 3 to 3000, more preferably 50 to 2000 from the viewpoint of handling and strength reinforcement.
  • the component (B) carbon fiber, carbon nanotube, or the like can be used.
  • the type of carbon fiber is not particularly limited, and various types such as polyacrylonitrile (PAN) -based, pitch-based, cellulose-based, and lignin-based are included.
  • PAN-based or pitch-based carbon fibers are preferably used from the viewpoint of strength reinforcement. From the viewpoint of improving handling properties, it is preferable to use one having a fiber length of 3 to 6 mm bundled with a sizing agent.
  • the sizing agent refers to a sizing agent that is added to the carbon fiber for the purpose of dispersing the carbon fiber in the resin and improving handling properties.
  • the sizing agent from the viewpoint of dispersibility in the resin, it is preferable to use epoxy, urethane, or a converging agent using a combination of epoxy and urethane.
  • (B) component contains the said sizing agent and carbon fiber.
  • the fiber diameter is preferably in the range of 5 to 15 ⁇ m, more preferably in the range of 5 to 12 ⁇ m, and still more preferably in the range of 6 to 10 ⁇ m.
  • the impregnation ratio of the sizing agent is preferably 3% by mass or less, more preferably 1 to 3% by mass with respect to the entire carbon fiber (100% by mass).
  • Commercially available products include NPS chopped fiber (manufactured by Nippon Polymer Co., Ltd., PAN-based carbon fiber, sizing agent: 1.75% epoxy urethane, fiber length: 6 mm), trading card (registered trademark) (manufactured by Toray Industries, Inc., PAN-based carbon) Fiber, sizing agent: urethane 3.0%, fiber length: 6 mm), Pyrofil (registered trademark) (manufactured by Mitsubishi Rayon Co., Ltd., PAN-based carbon fiber, sizing agent: 3.0%, fiber length: 6 mm) It is done.
  • both single-walled carbon nanotubes having a structure in which a graphite layer is wound in one layer, multi-walled carbon nanotubes having a structure in which two or more layers are wound, and multi-walled carbon nanotubes are used. It is preferable.
  • the fiber diameter and fiber length are not particularly limited as long as they have the effects of the present invention and have an aspect ratio of 3.0 to 250. Examples of commercially available products include VGCF (registered trademark) and VGCF-X (registered trademark) (both manufactured by Showa Denko KK).
  • the component (B) one type may be used alone, or two or more types may be used in combination.
  • the content of the component (B) in the resin composition is not particularly limited as long as it has the effects of the present invention, but it is preferably 3 to 25 parts by weight with respect to 100 parts by weight of the component (A), and 3 to 20 parts by weight. More preferably, it is 3 to 15 parts by mass, particularly preferably 4 to 15 parts by mass.
  • the content of the component (B) is less than 3 parts by mass with respect to 100 parts by mass of the component (A), it becomes difficult to obtain sufficient conductivity. Moreover, when it exceeds 25 mass parts, it will be easy to cause a fall of impact resistance.
  • the content of the component (B) in the resin composition is preferably 2 to 25% by mass, more preferably 3 to 20% by mass when the entire resin composition is 100% by mass, It is particularly preferably 3 to 12% by mass.
  • the content of the component (B) is less than 2% by mass, it is difficult to obtain sufficient conductivity.
  • content of (B) component exceeds 25 mass%, it will be easy to cause a fall of impact resistance. That is, when the content of the component (B) is 3 to 25 parts by mass with respect to 100 parts by mass of the component (A), or 2 to 25% by mass when the total resin composition is 100% by mass. If it exists, sufficient electroconductivity is acquired and since the impact resistance of a molded object does not fall, it is preferable.
  • the component (C) mainly contributes to improvement of mechanical strength (impact strength).
  • “Elastomer” means a polymer substance that is an elastic body at room temperature (25 ° C.).
  • the polymer material may be a natural polymer material or a synthetic polymer material.
  • the olefin-based elastomer (hereinafter also referred to as “component (C1)”) is composed of carbon atoms and hydrogen atoms obtained by polymerizing the olefin using olefin as a monomer, and has no aromatic ring.
  • component (C1) is composed of carbon atoms and hydrogen atoms obtained by polymerizing the olefin using olefin as a monomer, and has no aromatic ring.
  • Styrenic elastomer (hereinafter also referred to as “(C2) component”) is a styrene-based monomer having butadiene, butylene, or the like as a monomer, and having an aromatic ring in the main chain obtained by polymerizing the monomer, at room temperature ( A polymer substance that is an elastic material at 25 ° C.) and is typified by an aromatic vinyl-conjugated diene block copolymer.
  • the styrene elastomer is preferably styrene / butadiene / styrene (SBS), styrene / butadiene / butylene / styrene (SBBS), or styrene / ethylene / butylene / styrene (SEBS).
  • SBS styrene / butadiene / styrene
  • SBBS styrene / butadiene / butylene / styrene
  • SEBS styrene / ethylene / butylene / styrene
  • each of the (C1) component or the (C2) component may be used alone or in combination of two or more, and the (C1) component and the (C2) component are used in combination. May be.
  • the content of the component (C) in the resin composition is 5 to 25 parts by weight, preferably 5 to 20 parts by weight, and preferably 7 to 20 parts by weight with respect to 100 parts by weight of the component (A). Is more preferably 7 to 15 parts by mass, and most preferably 9 to 15 parts by mass.
  • the content of the component (C) is less than 5 parts by mass, the effect of improving the impact resistance is not sufficient, and when it exceeds 25 parts by mass, the heat resistance and the mechanical strength are likely to be reduced. In addition, the amount of outgas generated increases.
  • the content of the component (C) in the resin composition is preferably 2 to 22% by mass, more preferably 3 to 20% by mass when the entire resin composition is 100% by mass. If the content of the component (C) in the resin composition is less than 2% by mass, the effect of improving the impact resistance is not sufficient, and if it exceeds 22% by mass, the heat resistance is lowered and the mechanical strength is lowered. It is easy to invite. In addition, the amount of outgas generated increases. That is, when the content of the component (C) in the resin composition is 5 to 25 parts by mass with respect to 100 parts by mass of the component (A), or when the entire resin composition is 100% by mass. The content of 2 to 22% by mass is preferable because the heat resistance and mechanical strength of the resin composition do not decrease and the amount of outgas generated can be reduced.
  • the intrinsic viscosity is measured by a method according to JIS K7367-3 (1999).
  • the viscosity average molecular weight of the component (D) is 1 million or more, preferably 1 million or more and 6 million or less, more preferably 1 million or more and 4 million or less, particularly preferably 1.2 million or more and 4 million or less, Preferably they are 1.5 million or more and 4 million or less.
  • the viscosity average molecular weight of (D) component is 1 million or more, the abrasion resistance with respect to a wafer etc. and weld adhesiveness will improve.
  • the weld adhesion is improved because the viscosity of the resin composition increases due to the viscosity average molecular weight of the component (D) being 1 million or more, and the adhesion between the resin compositions on the weld surface is improved. it is conceivable that.
  • the impact strength and fluidity of the resin composition are easily maintained favorably. Also, the amount of outgas generated is small.
  • welding adhesiveness means a state of occurrence of a line (weld line) generated in a portion where a molten resin composition joins in a mold, and the weld line of the obtained molded body is defined as a weld line. Evaluation was performed by visual confirmation.
  • the component (D) in the resin composition, as the component (D), one type may be used alone, or two or more types may be used in combination.
  • the component (D) is preferably in the form of a powder having a particle size of about 10 to 50 ⁇ m because it can be more uniformly mixed.
  • the “particle diameter” refers to a value measured using a Coulter counter TA-II type, Nikki Co., Ltd. under the condition that component (D) is dispersed in water.
  • a commercial item can be used for a component.
  • Hi-Zex Million registered trademark
  • Mipperon registered trademark
  • polyethylene having a viscosity average molecular weight of 1 million or more and 4 million or less
  • miperon made by Mitsui Chemicals is more preferable.
  • the effect of improving wear resistance and weld adhesion is not sufficient, and when the content exceeds 18% by mass, It tends to cause a decrease in fluidity. That is, if the content of the component (D) in the resin composition is 1 to 20 parts by mass with respect to 100 parts by mass of the component (A), or a total of 100 parts by mass of the components (A) to (C) 1 to 20 parts by mass or the content of the component (D) in the resin composition is 0.4 to 18% by mass when the entire resin composition is 100% by mass. For example, the effect of improving the wear resistance and weld adhesion can be sufficiently obtained, and the fluidity is unlikely to be lowered when formed into a molded body, which is preferable.
  • the component (B) forms a non-uniform conductive network at a low addition amount
  • the component (E) forms a uniform conductive network even at a low addition amount. It is because it acts on.
  • surface resistivity refers to a value measured under the conditions of ASTM D257 using MCP-HT260 Hiresta IP manufactured by Mitsubishi Chemical Analytech.
  • the curvature amount at the time of setting it as a molded object can be reduced (the generation
  • the component (E) refers to a conductive filler having an aspect ratio (length (major axis of particles) / width (minor axis of particles)) of less than 3.
  • the aspect ratio of the component (E) is preferably 1 or more and less than 3, and more preferably 1 or 2.
  • carbon black, graphite or the like can be used as the component (E). Among these, carbon black is preferable because a conductive network can be formed in the resin composition with a small addition amount and the impact strength is not impaired.
  • the component (E) one type may be used alone, or two or more types may be used in combination.
  • a commercial item can be used for a component.
  • the commercial products include Ketjen Black EC 300J (manufactured by Lion Corporation, primary particle diameter 40 nm), Ketjen Black EC 600JD (manufactured by Lion Corporation, primary particle diameter 34 nm), Vulcan XC-72 (manufactured by Cabot Corporation, primary A particle diameter of 37 nm), Denka Black (manufactured by Denki Kagaku Kogyo Co., Ltd., primary particle diameter of 43 nm) (all are trade names) and the like can be suitably used.
  • the content of the component (E) in the resin composition is preferably 1 to 15 parts by weight, more preferably 1 to 12 parts by weight, with respect to 100 parts by weight of the component (A). Part is particularly preferred.
  • the content of the component (E) is less than the preferred lower limit with respect to 100 parts by mass of the component (A)
  • the content of the component (E) in the resin composition is preferably 1 to 12 parts by mass, and preferably 1 to 10 parts by mass with respect to 100 parts by mass in total of the components (A) to (C). Is more preferably 5 to 10 parts by mass.
  • the content of the component (E) is less than the preferred lower limit with respect to a total of 100 parts by mass of the components (A) to (C)
  • the effect of stabilizing the surface resistivity when formed into a molded product, and molding caused by molding The effect of suppressing the warp of the body is not sufficiently obtained, and when the preferable upper limit is exceeded, the impact resistance is likely to be lowered.
  • the content of the component (E) in the resin composition is preferably 0.4 to 15% by mass, and preferably 0.5 to 13% by mass when the entire resin composition is 100% by mass. Is more preferably 1 to 12% by mass, and more preferably 1 to 10% by mass.
  • the content of the component (E) is less than the preferred lower limit, it is difficult to sufficiently obtain the effect of stabilizing the conductivity when forming a molded body and the effect of suppressing warpage of the molded body caused by molding. If the upper limit is exceeded, impact resistance tends to be reduced. Moreover, there is a risk of becoming a source of contamination.
  • the content of the component (E) in the resin composition is 1 to 15 parts by mass relative to 100 parts by mass of the component (A), or a total of 100 parts by mass of the components (A) to (C)
  • the amount is 1 to 12 parts by mass, or 0.4 to 15% by mass when the entire resin composition is 100% by mass, the surface resistivity is stabilized when the molded body is formed. And the effect of suppressing warpage of the molded product produced by molding can be sufficiently obtained, impact resistance is not lowered, and component (E) itself is not likely to become a contamination source, which is preferable.
  • the total content of the component (B) and the component (E) in the resin composition is 5 to 25% by mass when the total resin composition is 100% by mass. It is preferably 5 to 18% by mass.
  • the total content of the component (B) and the component (E) is less than the preferred lower limit, it is difficult to obtain desired conductivity, and when it exceeds the preferred upper limit, impact resistance tends to be lowered. . That is, if the total content of the component (B) and the component (E) is 5 to 25% by mass when the entire resin composition is 100% by mass, desired conductivity can be obtained, and It is preferable because the impact resistance of the molded body is difficult to decrease.
  • the content ratio ((B) component content / (E) component content) of (B) component and (E) component is 3.0 or less, the effect of curvature suppression is high and preferable.
  • the resin composition of the present invention can be produced by melt kneading the above-described components using a known resin kneading equipment (for example, a heat roll, a kneader, a Banbury mixer, etc.) or a twin-screw kneading extruder. If necessary, a pelletized resin composition may be formed using a pelletizer. What is necessary is just to set suitably the temperature at the time of melt-kneading the component mentioned above according to the kind of cyclic olefin homopolymer (A) to be used, and it is 200-400 degreeC normally.
  • a known resin kneading equipment for example, a heat roll, a kneader, a Banbury mixer, etc.
  • a twin-screw kneading extruder e.g., a twin-screw kneading extruder.
  • a pelletized resin composition may
  • a molded object is obtained by performing injection molding, injection compression molding, compression molding, extrusion molding, or blow molding using the resin composition of the present invention (preferably a resin composition in the form of pellets). be able to.
  • the resin composition of the present invention preferably a resin composition in the form of pellets.
  • a method for manufacturing a semiconductor storage container includes a step of melting a resin composition of the present invention (preferably a pellet-shaped resin composition) to obtain a molten resin, and filling the mold with the molten resin
  • the method preferably includes a step of obtaining a molded body.
  • the temperature for melting the resin composition of the present invention is preferably 260 to 300 ° C.
  • the mold temperature is preferably 50 to 100 ° C.
  • the molding temperature is preferably 260 to 290 ° C.
  • the mechanical strength is high, and the wafer and the like can be protected from impact caused by contact with other members.
  • heat resistance is high, and when a molded body is dried, deformation due to heat can be prevented.
  • a resin composition of the present invention is particularly suitable as an electronic component packaging container used in an electronic component manufacturing process in which low outgassing is strongly desired as semiconductor circuit patterns become finer.
  • it is suitable for a semiconductor storage and conveyance container.
  • A′-1 Cyclic olefin homopolymer, manufactured by Nippon Zeon Co., Ltd., trade name “ZEONOR (registered trademark) 1060R”, Tg is 100 ° C.
  • A′-2 Cyclic olefin homopolymer, manufactured by Nippon Zeon Co., Ltd., trade name “ZEONOR (registered trademark) 1600”, Tg: 163 ° C.
  • A′-3 Cyclic olefin copolymer, manufactured by Mitsui Chemicals, trade name “Apel (registered trademark) 5014DP”, Tg: 135 ° C.
  • [Fibrous conductive filler (B)] B-1 Carbon fiber, manufactured by Nippon Polymer Co., Ltd., trade name “EPU-LCL”. The fiber diameter is 7.0 ⁇ m, and the fiber length is 6.0 mm (aspect ratio 857).
  • C At least one elastomer (C) selected from the group consisting of olefin elastomers and styrene elastomers]
  • C-1 Styrene elastomer, manufactured by Asahi Kasei Chemical Co., Ltd., trade name “Tuftec (registered trademark) H1053”.
  • C-2 Olefin-based elastomer, manufactured by Mitsui Chemicals, Inc., trade name “Tuffmer (registered trademark) A4085S”.
  • C′-1 Polyester elastomer, manufactured by Toyobo Co., Ltd., trade name “Perprene (registered trademark) P150M”.
  • D-1 Ultra high molecular weight polyethylene, manufactured by Mitsui Chemicals, trade name “Miperon (registered trademark) XM-220”; viscosity average molecular weight 2 million, average particle size 30 ⁇ m.
  • Comparison component (D ′) of component (D)] D′-1 polyethylene having a viscosity average molecular weight of less than 1 million (high density polyethylene), manufactured by Prime Polymer Co., Ltd., trade name “Hi-Zex (registered trademark) 2208J”; viscosity average molecular weight of about 65,000.
  • E-1 Carbon black, manufactured by Lion Corporation, trade name “Ketjen Black (registered trademark) EC300J”; particle size (primary particle size) 40 nm, aspect ratio of about 1, n-dibutyl phthalate (DBP) oil absorption 360 mL / 100 g.
  • E′-1 Carbon black, manufactured by Denki Kagaku Kogyo Co., Ltd., trade name “Denka Black (registered trademark)”; particle size (primary particle size) 43 nm, n-dibutyl phthalate (DBP) oil absorption 165 mL / 100 g.
  • Example 1 Using a twin screw extruder NR-II (manufactured by Nakatani Machinery Co., Ltd., screw diameter: 57 mm), a pre-blended mixture of component (A) and component (C) is supplied from the former hopper of the extruder, and the mixture was completely melted at 280 ° C., component (B) was forcibly supplied to the extruder through a side feeder using a quantitative feeder and kneaded to obtain a compound. Next, after cooling the compound, a cylindrical pellet (diameter 2 mm, length 2 to 4 mm) was prepared using a pelletizer (manufactured by Nakatani Machinery Co., Ltd., GF5).
  • a pelletizer manufactured by Nakatani Machinery Co., Ltd., GF5
  • Example 5 A cylindrical pellet was prepared in the same manner as in Example 1 except that the composition was changed to the composition shown in Table 1.
  • Example 6 (Examples 6 and 7) Using a twin-screw extruder NR-II (manufactured by Nakatani Machinery Co., Ltd., screw diameter 57 mm), a pre-blended mixture of component (A), component (C) and component (D) was transferred from the former hopper of the extruder. When the mixture was completely melted, the compound (B) was forcibly supplied to the extruder through a side feeder using a quantitative feeder and kneaded to obtain a compound. Next, after cooling this compound, cylindrical pellets were prepared in the same manner as in Example 1.
  • NR-II manufactured by Nakatani Machinery Co., Ltd., screw diameter 57 mm
  • Example 8 A cylindrical pellet was prepared in the same manner as in Example 6 except that the component was changed to the comparative component (D ′).
  • Example 9 A cylindrical pellet was prepared in the same manner as in Example 1 except that the component (E) was supplied together with the component (B) through the side feeder by the quantitative feeder.
  • Example 11 Cylindrical pellets were prepared in the same manner as in Examples 6 and 7, except that the component (E) was supplied together with the component (B) through the side feeder using a quantitative feeder.
  • Example 12 Columnar pellets were prepared in the same manner as in Examples 9 and 10 except that the component (E) was changed to the comparative component (E ′).
  • Component is not blended, that is, using a twin screw extruder NR-II (manufactured by Nakatani Machinery Co., Ltd., screw diameter 57 mm), a mixture of (A) component and (C) component pre-blended in advance
  • the compound was obtained by supplying from the former hopper of the machine and melt-kneading. Next, after cooling this compound, cylindrical pellets were prepared in the same manner as in Example 1.
  • Example 3 A cylindrical pellet was prepared in the same manner as in Example 1 except that the composition was changed to the composition shown in Table 1.
  • Example 5 A columnar pellet was prepared in the same manner as in Example 2 except that the component (B) was changed to the comparative component (B ′).
  • test piece Using an injection molding machine (manufactured by Nissei Plastic Industry Co., Ltd., FS120EM25ASE), from the resin composition (cylindrical pellet) of each example prepared in the above production example, a dumbbell test piece for strength measurement (ISO standard multipurpose test piece) A), a flat plate for measuring conductivity (76 mm ⁇ 76 mm ⁇ 3.2 mm), and a test piece (310 mm ⁇ 360 mm ⁇ 20 mm) for evaluation of warpage suppression of the molded body were molded by a conventional method, and each evaluation A test piece was prepared for use.
  • the molding temperature was 250 to 280 ° C, and the mold temperature was set to 50 ° C.
  • the deflection temperature under load was measured by a method based on ISO 75-2Af as an index of heat resistance. The case where the deflection temperature under load was 95 ° C. or higher was regarded as acceptable. The higher the deflection temperature under load, the better the heat resistance.
  • the surface resistivity was measured by a method based on ASTM D257 as a conductivity index. A case where the surface resistivity was 1.0E + 4 to 1.0E + 10 (1.0 ⁇ 10 4 to 1.0 ⁇ 10 10 ) ⁇ was regarded as acceptable.
  • the amount of outgas generated as an indicator of low outgassing property was measured by the following method. Weigh out 5.0 g of the resin composition (cylindrical pellet) of each example, collect it in a test tube, and measure the amount of outgas generated when heated at 150 ° C. for 1 hour using a gas chromatograph mass spectrometer (GC-MS). And measured by the headspace (HS) method. The amount of volatile gas generated was converted from the relative concentration using phenol, and the value calculated as the concentration per unit mass was defined as the outgas generation amount.
  • GC-MS gas chromatograph mass spectrometer
  • HS headspace
  • the amount of volatile gas generated was converted from the relative concentration using phenol, and the value calculated as the concentration per unit mass was defined as the outgas generation amount.
  • the measuring apparatus 5890 manufactured by HP as a gas chromatography apparatus and 5972 manufactured by HP as a mass spectrometer were used. A case where the amount of outgas generated was less than 40 ppm was regarded as acceptable. The
  • Wafer sliding load was measured by conducting a wafer sliding wear test as an index of wear resistance. Using an amplitude tester, the cleaned and dried injection molded test piece (20 mm ⁇ 40 mm ⁇ 3 mm) was brought into contact with the outer peripheral portion (peripheral surface) of a 300 mm diameter silicon wafer. The reciprocating test was conducted 100,000 times. After the end of the reciprocating test, the amplitude tester was removed, and the peripheral surface of the silicon wafer that was in contact with the injection-molded test piece was connected to a tensile tester positioned vertically upward via a pulley. Then, the tensile load was measured at a constant speed, and the value was defined as the wafer sliding load (N).
  • Tensilon RTC-1325A (manufactured by ORIENTEC) was used as the tensile tester. If the wafer sliding load is within 0.40N, it is A. If it is better than 0.40N, B is better if it is within 0.40N but less than 0.60N, and if it is more than 0.60N, it is bad. As C, wear resistance was evaluated.
  • weld adhesion is a line (weld line) formed at a portion where a molten resin composition is joined when a cubic container (width 430 mm ⁇ length 356 mm ⁇ height 339 mm) is manufactured by injection molding from one gate. ) Occurrence state (appearance of the container) was observed visually. The weld adhesion was evaluated with A as the case where substantial weld lines were not observed, B as the case where weld lines were slightly observed, and C as the case where weld lines were clearly observed.
  • the standard deviation (variation) of the surface resistivity was determined as an index for stabilizing the conductivity (antistatic ability).
  • a flat plate (76 mm ⁇ 76 mm ⁇ 3.2 mm) for conductivity measurement was divided into six locations, and the surface resistivity of each division was measured.
  • the surface resistivity was measured using an MCP-HT260 Hiresta IP manufactured by Mitsubishi Chemical Analytech Co., Ltd. with an electrode-shaped URS probe.
  • the common logarithm of the surface resistivity of each category was calculated, and their standard deviation (variation) was analyzed. When the standard deviation of the logarithm of the surface resistivity is less than 0.03, the conductivity stability is better as A. When the standard deviation is 0.03 or more and less than 0.10, the conductivity stability is good. Assuming that B is 0.10 or more, C is regarded as having a variation in conductivity, and the conductivity stability was evaluated.
  • Example 9 containing E-1 having a DBP oil absorption of 180 mL or more is more than Example 12 containing E′-1 having a DBP oil absorption of less than 180 mL. It can be seen that, although the amount of the particulate conductive filler used is small, the same conductivity is exhibited, and the warpage of the molded body caused by stabilization of the conductivity and molding is achieved.
  • the resin composition of the present invention it is possible to provide a molded article having excellent mechanical strength, heat resistance, conductivity and low outgassing properties.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Cette invention concerne une composition de résine qui est caractérisée en ce qu'elle contient (A) un homopolymère d'oléfine cyclique qui a une température de transition vitreuse de 101 à 160°C, (B) une charge conductrice fibreuse, et (C) au moins un élastomère qui est choisi dans le groupe constitué par les élastomères à base d'oléfine et les élastomères à base de styrène. Cette composition de résine est également caractérisée en ce que la teneur de l'élastomère (C) est de 5 à 25 parties en poids pour 100 parties en poids de l'homopolymère d'oléfine cyclique (A). Cette invention permet d'obtenir une composition de résine capable de donner un corps moulé ayant une excellente résistance mécanique, résistance thermique, conductivité électrique et d'excellentes propriétés de faible dégazage.
PCT/JP2013/059591 2012-04-04 2013-03-29 Composition de résine WO2013150979A1 (fr)

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CN201380018465.3A CN104245832B (zh) 2012-04-04 2013-03-29 树脂组合物
MYPI2014702847A MY184861A (en) 2012-04-04 2013-03-29 Resin composition

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TWI644965B (zh) * 2013-12-04 2018-12-21 迪睿合股份有限公司 Cyclic olefin resin composition film
US20210301079A1 (en) * 2018-07-19 2021-09-30 Zeon Corporation Shaping material and shaped product

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JP6031625B1 (ja) * 2016-03-11 2016-11-24 クオドラントポリペンコジャパン株式会社 樹脂組成物及び成形体
CN113646385B (zh) * 2019-03-26 2024-02-27 日商Mcc先进成型股份有限公司 树脂组合物
KR20230049082A (ko) 2020-08-12 2023-04-12 니폰 제온 가부시키가이샤 수지 조성물 및 그 제조 방법, 성형 재료, 포장 용기, 그리고 반도체 용기

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US20210301079A1 (en) * 2018-07-19 2021-09-30 Zeon Corporation Shaping material and shaped product

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CN104245832A (zh) 2014-12-24
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KR20140147822A (ko) 2014-12-30
MY184861A (en) 2021-04-28
JP2013231171A (ja) 2013-11-14
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TW201345968A (zh) 2013-11-16
CN104245832B (zh) 2017-01-18

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