WO2022158599A1 - 樹脂組成物、樹脂成形体及びその製造方法 - Google Patents
樹脂組成物、樹脂成形体及びその製造方法 Download PDFInfo
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- B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
- B29K2023/10—Polymers of propylene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2101/00—Use of unspecified macromolecular compounds as moulding material
- B29K2101/12—Thermoplastic materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
- B29K2105/12—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of short lengths, e.g. chopped filaments, staple fibres or bristles
- B29K2105/14—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of short lengths, e.g. chopped filaments, staple fibres or bristles oriented
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
- B29K2105/16—Fillers
- B29K2105/18—Fillers oriented
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2307/00—Use of elements other than metals as reinforcement
- B29K2307/04—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0012—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular thermal properties
- B29K2995/0013—Conductive
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
- C08J2323/12—Polypropene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- 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
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- 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
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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- 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
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
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- 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
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
Definitions
- the present invention relates to a resin composition, a resin molding using the resin composition, and a method for producing the resin molding.
- Patent Document 1 discloses a molded product obtained by molding a resin compound containing a thermoplastic resin, graphite, and carbon black. Patent Document 1 describes that it is preferable to contain 20 to 80% by weight of graphite with respect to the entire resin compound. Further, it is described that it is preferable to contain 1 to 30% by weight of carbon black with respect to the entire resin compound.
- An object of the present invention is to provide a resin composition having excellent electromagnetic wave shielding properties, a resin molded article using the resin composition, and a method for producing the resin molded article.
- the resin composition according to the first invention of the present application contains a thermoplastic resin (A), graphite (B), and two or more types of carbon black (C), and the carbon black (C) has a BET ratio It contains a first carbon black (C-1) having a surface area of 600 m 2 /g or more and a second carbon black (C-2) having a BET specific surface area of less than 600 m 2 /g.
- the content of the first carbon black (C-1) is 5 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A). 50 parts by weight or less, the content of the second carbon black (C-2) is 5 parts by weight or more and 50 parts by weight or less, and the total content of the carbon black (C) is 15 parts by weight. It is 90 parts by weight or more and 90 parts by weight or less.
- the DBP oil absorption of the first carbon black (C-1) is 250 ml/100 g or more
- the second carbon black ( C-2) has a DBP oil absorption of less than 250 ml/100 g.
- the carbon black (C) has an ash content of 1% or less.
- the graphite (B) is plate-like graphite.
- the graphite (B) has a volume average particle size of 5 ⁇ m or more and 500 ⁇ m or less.
- the content of the graphite (B) is 50 parts by weight or more and 300 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A). It is below the department.
- thermoplastic resin (A) is at least one of an olefin-based resin and a nylon-based resin.
- the specific volume resistivity is 1.0 ⁇ 10 5 ⁇ cm or less.
- a resin composition according to a second invention of the present application is a resin composition containing a thermoplastic resin (A), graphite (B), and carbon black (D), and is melted in a mold.
- the resin composition was filled in the direction perpendicular to the thickness direction of the resin molded body to obtain the resin composition and molded to obtain a resin molded body of 100 mm long ⁇ 100 mm wide ⁇ 2 mm thick, it was measured at 125 ° C. using pulse NMR.
- the spin-spin relaxation free induction decay curve of 1 H obtained by measuring the resin molded body by the Hahn Echo method is analyzed by the least squares method to determine the three components of the S component, the M component, and the L component in the order of shortest relaxation time.
- the relaxation time of the L component is 1.3 msec or less when the waveform is separated into three curves respectively derived from .
- the ratio of the L component to the sum of the S component, the M component, and the L component is 10% or less.
- the ratio of the L component to the sum of the S component, the M component, and the L component is 4% or more.
- the graphite (B) is plate-like graphite.
- thermoplastic resin (A) contains an olefin resin.
- the first and second inventions of the present application may be collectively referred to as the present invention.
- the resin composition obtained in a molten state is filled in a mold from a direction perpendicular to the thickness direction of the resin molded body to be molded.
- the electromagnetic wave shielding effect of the resin molded body at any frequency of 3 GHz, 25 GHz, 50 GHz and 75 GHz is 20 dB or more.
- the resin composition obtained in a molten state is filled in a mold from a direction perpendicular to the thickness direction of the resin molded body to be molded.
- the thermal conductivity in the in-plane direction of the resin molded body is 1 W/(m ⁇ K) or more.
- a resin molded article according to the present invention is a molded article of a resin composition configured according to the present invention.
- the resin molded article contains fibers.
- the volume resistivity is 1.0 ⁇ 10 5 ⁇ cm or less.
- the method for producing a resin molded article according to the present invention includes the step of mixing a resin composition configured according to the present invention with a composite (E) containing a thermoplastic resin and fibers to obtain a mixture, and molding the mixture. and a step of obtaining a resin molded body.
- the present invention it is possible to provide a resin composition having excellent electromagnetic wave shielding properties, a resin molded article using the resin composition, and a method for producing the resin molded article.
- FIG. 1 is a schematic perspective view showing a heat dissipation chassis.
- FIG. 2 is a schematic perspective view showing a heat dissipation housing.
- FIG. 3 is a schematic perspective view showing the shape of a heat sink.
- the resin composition of the first invention contains a thermoplastic resin (A), graphite (B), and two or more types of carbon black (C).
- the carbon blacks (C) are a first carbon black (C-1) having a BET specific surface area of 600 m 2 /g or more and a second carbon black (C-2) having a BET specific surface area of less than 600 m 2 /g. and
- the BET specific surface area can be measured from the nitrogen adsorption isotherm in accordance with the BET method.
- a measuring device for example, product number "NOVAtouchLX2" manufactured by Anton Paar can be used.
- the resin composition of the first invention contains a thermoplastic resin (A), graphite (B), and two or more types of specific carbon black (C), it is excellent in both electromagnetic shielding properties and moldability. ing.
- the present inventors have found that in a resin composition containing a thermoplastic resin (A), graphite (B), and two or more types of carbon black (C), the first carbon black (C-1) and the second Focusing on the BET specific surface area of the carbon black (C-2) of No. 2.
- the present inventors used a first carbon black (C-1) having a BET specific surface area of 600 m 2 /g or more and a second carbon black (C-2) having a BET specific surface area of less than 600 m 2 /g. It was found that by using carbon black (C) containing and, both the electromagnetic wave shielding property and the moldability of the resin composition can be improved.
- thermoplastic resin is not particularly limited, and known thermoplastic resins can be used. Specific examples of thermoplastic resins include polyolefins, polystyrenes, polyacrylates, polymethacrylates, polyacrylonitrile, polyesters, polyamides, polyurethanes, polyethersulfones, polyetherketones, polyimides, polydimethylsiloxanes, polycarbonates, or at least two of these. Seed-containing copolymers, and the like. These thermoplastic resins may be used alone or in combination. It should be noted that the thermoplastic resin is preferably a resin having a high elastic modulus. Polyolefin (olefin-based resin) and polyamide (nylon-based resin) are more preferable because they are inexpensive and easy to mold under heat.
- the polyolefin is not particularly limited, and known polyolefins can be used.
- Specific examples of polyolefins include polyethylene, which is an ethylene homopolymer, ethylene- ⁇ -olefin copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid ester copolymer, ethylene-acetic acid.
- Examples include polyethylene resins such as vinyl copolymers.
- the polyolefin is a propylene homopolymer such as polypropylene, a polypropylene-based resin such as a propylene- ⁇ -olefin copolymer, a butene homopolymer such as polybutene, butadiene, or a conjugated diene homopolymer or copolymer such as isoprene. and so on. These polyolefins may be used alone or in combination. From the viewpoint of further increasing the heat resistance and elastic modulus, the polyolefin is preferably polypropylene.
- the polyolefin (olefin resin) preferably contains an ethylene component.
- the content of the ethylene component is preferably 5% by mass to 40% by mass. When the content of the ethylene component is within the above range, it is possible to further improve the heat resistance while further improving the impact resistance of the resin molding.
- the MFR of the thermoplastic resin measured according to JIS K7210 is preferably 10 g/10 min or more, more preferably 30 g/10 min or more, preferably 200 g/10 min or less, more preferably 150 g/10 min or less. be. When the MFR is within the above range, the fluidity of the thermoplastic resin can be further enhanced.
- the content of the thermoplastic resin in the resin composition is preferably 20% by weight or more, more preferably 25% by weight or more, preferably 65% by weight or less, and more preferably 60% by weight or less.
- the content of the thermoplastic resin is within the above range, the moldability of the resin composition can be further enhanced.
- the graphite is not particularly limited, but plate-like graphite is preferable.
- the plate-like graphite is not particularly limited as long as it is plate-like graphite, and for example, graphite, exfoliated graphite, or graphene can be used.
- Graphite or exfoliated graphite is preferred from the viewpoint of further enhancing thermal conductivity and flame retardancy. These may be used alone or in combination.
- scale-like graphite can be used as plate-like graphite, for example. Expanded graphite may be used from the viewpoint of further enhancing flame retardancy.
- Exfoliated graphite is obtained by exfoliating the original graphite, and refers to a graphene sheet laminate that is thinner than the original graphite.
- the exfoliation treatment for exfoliating graphite is not particularly limited, and either a mechanical exfoliation method using a supercritical fluid or the like or a chemical exfoliation method using an acid may be used.
- the number of laminated graphene sheets in exfoliated graphite should be less than that of the original graphite, but is preferably 1000 or less, more preferably 500 or less, and even more preferably 200 or less.
- the volume average particle size of the plate-like graphite is preferably 5 ⁇ m or more, more preferably 30 ⁇ m or more, still more preferably 60 ⁇ m or more, preferably 500 ⁇ m or less, more preferably 350 ⁇ m or less, further preferably 300 ⁇ m or less. be.
- the volume average particle size of the plate-like graphite is at least the above lower limit, the electromagnetic wave shielding properties and heat dissipation properties can be further enhanced.
- the volume average particle size of the plate-like graphite is equal to or less than the above upper limit, the impact resistance of the resin molded article can be further enhanced.
- the volume average particle size of the plate-like graphite contained in the resin composition of the first invention is within the above range, two or more types of graphite particles having different particle sizes may be used in combination.
- the volume average particle size is a value calculated from a volume standard distribution by a laser diffraction method using a laser diffraction/scattering particle size distribution measuring device in accordance with JIS Z 8825:2013. Say.
- plate-like graphite is put into a soapy water solution (neutral detergent: containing 0.01%) so that its concentration becomes 2% by weight, and ultrasonic waves are applied for 1 minute at an output of 300 W using an ultrasonic homogenizer. , to obtain a suspension.
- the suspension is measured for the volume particle size distribution of the plate-like graphite by a laser diffraction/scattering particle size analyzer (manufactured by Nikkiso Co., Ltd., product name “Microtrac MT3300”).
- the cumulative 50% value of this volume particle size distribution can be calculated as the volume average particle size of the plate-like graphite.
- the content of the plate-like graphite is preferably 50 parts by weight or more, more preferably 70 parts by weight or more, still more preferably 100 parts by weight or more, and preferably 300 parts by weight or less, with respect to 100 parts by weight of the thermoplastic resin. It is preferably 250 parts by weight or less, more preferably 200 parts by weight or less.
- the content of plate-like graphite is at least the above lower limit, the electromagnetic wave shielding properties and heat dissipation properties can be further enhanced.
- the content of plate-like graphite is too large, the area of the interface, which is the starting point of fracture, becomes large. can.
- the aspect ratio of the plate-like graphite is preferably 5 or more, more preferably 21 or more, preferably less than 2000, more preferably less than 1000, still more preferably less than 100.
- the aspect ratio of the plate-like graphite is equal to or higher than the above lower limit, heat dissipation in the planar direction can be further enhanced.
- the aspect ratio of the plate-like graphite is less than the above upper limit, the graphite particles themselves are less likely to bend in the thermoplastic resin during injection molding, for example. Therefore, the electromagnetic wave shielding performance can be further enhanced.
- the aspect ratio refers to the ratio of the maximum dimension of the plate-like graphite in the stacking plane direction to the thickness of the plate-like graphite.
- the thickness of plate-like graphite can be measured using, for example, a transmission electron microscope (TEM) or a scanning electron microscope (SEM). From the viewpoint of making observation easier, a test piece cut out from the resin composition or resin molded body is heated at 600 ° C. to blow off the resin and observed with a transmission electron microscope (TEM) or a scanning electron microscope (SEM). It is desirable to In addition, the test piece may be cut out along the direction along the main surface of the resin molded body as long as the thickness of the plate-like graphite can be measured by skipping the resin, or along the direction perpendicular to the main surface of the resin molded body. You can cut it out.
- TEM transmission electron microscope
- SEM scanning electron microscope
- Carbon black (C) first carbon black (C-1);
- first carbon black for example, oil furnace black such as Ketjen black, acetylene black, channel black, thermal black and the like can be used. Among them, oil furnace black is preferable from the viewpoint of further increasing the conductivity of the obtained resin molding.
- the ash content of carbon black is preferably 1% or less. Carbon black may also contain metal impurities such as Fe and Ni.
- the BET specific surface area of the first carbon black is 600 m 2 /g or more, preferably 700 m 2 /g or more, more preferably 800 m 2 /g or more.
- the upper limit of the BET specific surface area of the first carbon black can be, for example, 1800 m 2 /g, preferably 1600 m 2 /g or less, more preferably 1200 m 2 /g or less.
- the DBP oil absorption of the first carbon black is not particularly limited, it is preferably 250 ml/100 g or more, more preferably 270 ml/100 g or more, and even more preferably 300 ml/100 g or more.
- the conductivity can be further enhanced.
- the upper limit of the DBP oil absorption of the first carbon black can be, for example, 600 ml/100 g.
- the DBP oil absorption of carbon black can be obtained by calculating the DBP drip amount at 70% of the maximum torque in accordance with JIS K 6217-4.
- the DBP oil absorption can be measured, for example, using an absorption measuring device (manufactured by Asahi Research Institute, product number “S-500”).
- the primary particle size of the first carbon black is not particularly limited, it is preferably 15 nm or more, more preferably 20 nm or more, preferably 60 nm or less, and more preferably 50 nm or less. When the primary particle size of the first carbon black is within the above range, a higher conductivity can be obtained with a lower content of the first carbon black.
- the primary particle size of carbon black is, for example, the average primary particle size obtained using image data of carbon black obtained by a transmission electron microscope.
- a transmission electron microscope for example, the product name "JEM-2200FS” manufactured by JEOL Ltd. can be used.
- the content of the first carbon black is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, preferably 50 parts by weight or less, more preferably 40 parts by weight or less with respect to 100 parts by weight of the thermoplastic resin. .
- the content of the first carbon black is at least the above lower limit, the conductivity can be further enhanced.
- the content of the first carbon black is equal to or less than the above upper limit, the fluidity during molding can be further improved, and the moldability can be further improved.
- oil furnace black such as Ketjen black, acetylene black, channel black, thermal black and the like can be used.
- oil furnace black is preferable from the viewpoint of further increasing the conductivity of the obtained resin molding.
- both the first carbon black and the second carbon black are more preferably oil furnace black.
- the ash content of carbon black is preferably 1% or less.
- Carbon black may also contain metal impurities such as Fe and Ni.
- the BET specific surface area of the second carbon black is less than 600 m 2 /g, preferably 400 m 2 /g or less, more preferably 300 m 2 /g or less.
- the lower limit of the BET specific surface area of the second carbon black can be, for example, 30 m 2 /g, preferably 100 m 2 /g or more, more preferably 150 m 2 /g or more.
- the DBP oil absorption of the second carbon black is not particularly limited, it is preferably less than 250 ml/100 g, more preferably 200 ml/100 g or less.
- the DBP oil absorption of the second carbon black is less than the upper limit or equal to or less than the upper limit, the fluidity during molding can be further improved, and the moldability can be further improved.
- the lower limit of the DBP oil absorption of the second carbon black can be set to 30 ml/100 g, for example.
- the primary particle size of the second carbon black is preferably 5 nm or more, more preferably 10 nm or more, still more preferably 15 nm or more, preferably 80 nm or less, more preferably 70 nm or less, still more preferably 60 nm or less, and particularly preferably 50 nm or less. is.
- the primary particle size of the second carbon black is within the above range, a higher conductivity can be obtained with a lower concentration of the second carbon black content.
- the content of the second carbon black is preferably 5 parts by weight or more, more preferably 10 parts by weight or more, preferably 50 parts by weight or less, more preferably 40 parts by weight or less with respect to 100 parts by weight of the thermoplastic resin. .
- the content of the second carbon black is at least the above lower limit, the fluidity during molding can be further improved, and the moldability can be further improved.
- the content of the second carbon black is equal to or less than the above upper limit, the conductivity can be further enhanced.
- the ratio (C-1)/(C-2) of the first carbon black to the second carbon black is preferably 0.01 or more, more preferably 0.1 or more, and still more preferably It is 0.5 or more, preferably 10 or less, more preferably 5 or less, and still more preferably 2 or less.
- (C-1)/(C-2) is at least the above lower limit, the conductivity can be further enhanced.
- (C-1)/(C-2) is equal to or less than the above upper limit, the fluidity during molding can be further improved, and the moldability can be further improved.
- the content of the entire carbon black is preferably 15 parts by weight or more, more preferably 25 parts by weight or more, preferably 90 parts by weight or less, more preferably 70 parts by weight or less with respect to 100 parts by weight of the thermoplastic resin. .
- the content of the entire carbon black is at least the above lower limit, the conductivity can be further enhanced.
- the content of the entire carbon black is equal to or less than the above upper limit, the fluidity during molding can be further improved, and the moldability can be further improved.
- the carbon black may further contain carbon black other than the first carbon black and the second carbon black.
- carbon blacks the carbon blacks described in the sections on the first carbon black and the second carbon black can be appropriately used.
- additives include, for example, phenol-based, phosphorus-based, amine-based, sulfur-based antioxidants; benzotriazole-based, hydroxyphenyltriazine-based UV absorbers; metal damage inhibitors; various fillers; stabilizers; pigments; These may be used alone or in combination.
- the resin composition described above comprises, first, a thermoplastic resin (A), graphite (B), a first carbon black (C-1) having a BET specific surface area of 600 m 2 /g or more, and a BET specific surface area of 600 m It can be obtained by melt-kneading the second carbon black (C-2) having a carbon black of less than 2 /g and, if necessary, other additives.
- the method of melt-kneading is not particularly limited.
- a method of kneading under the Among these, the method of melt-kneading using an extruder is preferable.
- the form of the resin composition of the first invention is not particularly limited, it can be, for example, a pellet.
- the shape is not particularly limited, but examples include spherical, cylindrical, and prismatic shapes. Among these, a columnar shape is preferable from the viewpoint of pellet shape stability.
- the diameter is preferably 0.5 mm or more, more preferably 1 mm or more, and preferably 5 mm or less, more preferably 3 mm or less.
- the length is preferably 1 mm or more, more preferably 3 mm or more, and preferably 10 mm or less, more preferably 7 mm or less.
- the size of the pellet can be measured by randomly collecting 100 pellets from the sample and using a vernier caliper.
- the diameter (pellet diameter) of the resin composition pellets other than cylindrical is preferably 1 mm or more, more preferably 5 mm or more, preferably 15 mm or less, and more preferably 10 mm or less.
- the pellet diameter can be obtained by randomly extracting 100 pellets from a sample and measuring the diameter at the longest point using a vernier caliper.
- the resin composition of the first invention preferably has a specific volume resistivity of 1.0 ⁇ 10 5 ⁇ cm or less, more preferably 1.0 ⁇ 10 2 ⁇ cm or less.
- the lower limit of the specific volume resistivity is not particularly limited, it is, for example, 1.0 ⁇ 10 ⁇ 4 ⁇ cm.
- the volume specific resistivity can be calculated from the resistivity correction factor and the thickness of the resin composition by measuring the resistance value using a low-resistance resistivity meter. For example, it can be measured at room temperature in the atmosphere using a four-probe resistivity measuring device (Loresta AX MCP-T370, manufactured by Mitsubishi Chemical Analytech).
- the resin composition of the second invention of the present application contains a thermoplastic resin (A), graphite (B), and carbon black (D).
- the relaxation time of the L component is 1.3 msec or less when the following measurement is performed using pulse NMR.
- the measurement by pulse NMR described above can be performed, for example, as follows. 700 mg of a resin molded sample obtained under the following molding conditions is introduced into a 10 mm diameter glass sample tube (manufactured by BRUKER, product number 1824511, 10 mm diameter, 180 mm length, flat bottom). Then, the sample tube is placed in a pulse NMR apparatus (“the minispe mq20” manufactured by BRUKER) and held at 125° C. for 10 minutes. After that, the Hahn Echo method was performed at 125° C., and the obtained 1 H spin-spin relaxation free induction decay curve was divided into three components, the S component, the M component, and the L component, in the order of shortest relaxation time by the least-squares method. The waveform is separated into three curves derived from each.
- the mold is filled with the molten resin composition of the second invention from the direction perpendicular to the thickness direction of the resin molding to obtain a resin molding of 100 mm long x 100 mm wide x 2 mm thick. .
- a sample of the resin molding is obtained by cutting the obtained flat plate of the resin molding into a 5 mm square.
- Waveform separation is performed by fitting using the exponential type.
- fitting is performed according to the product manual using analysis software "TD-NMRA (Version 4.3 Rev 0.8)" manufactured by BRUKER.
- w1 to w3 are Weibull coefficients, and w1, w2 and w3 take a value of 1.
- A1 is the S component
- B1 is the M component
- C1 is the L component ratio
- T2A is the S component
- T2B is the M component
- T2C is the L component's relaxation time.
- t is time.
- Final Plus Separation should preferably be set so that the strength of the normalized relaxation curve is 0.02 msec or less, and Recycle Deray should be five times the longitudinal relaxation time T1. It is desirable to set
- a free induction decay curve for 1 H spin-spin relaxation is obtained, typically measured by pulsed NMR.
- the obtained free induction decay curve can be waveform-separated into three curves derived from the three components of the S component, the M component, and the L component in order of shortest relaxation time. That is, the actually measured free induction attenuation curve is obtained by superimposing the free induction attenuation curve derived from the three components of the S component, M component and L component.
- Such a method of separating and analyzing three components using pulse NMR is known, and examples of documents describing the method include Japanese Patent Application Laid-Open No. 2018-2983.
- the S component is a component with a short relaxation time in pulse NMR measurement, meaning a hard component with low molecular mobility.
- the L component is a component with a long relaxation time in pulse NMR measurement, and means a soft component with high molecular mobility.
- the M component has a relaxation time in pulsed NMR measurements between the S and L components, so the molecular mobility is also between the S and L components.
- the resin composition of the second invention can improve long-term heat resistance because the relaxation time of the L component is 1.3 msec or less.
- the relaxation time of the L component is preferably 1.2 msec or less, more preferably 1.0 msec or less.
- the lower limit of the relaxation time of the L component is not particularly limited, it can be set to 0.5 msec, for example.
- the ratio of the L component to the sum of the S component, the M component, and the L component is preferably 4% or more, more preferably is 5% or more, preferably 10% or less, more preferably 9% or less.
- the ratio (L component/(S component+M component+L component)) is within the above range, long-term heat resistance can be further improved.
- the relaxation time and component ratio of the L component in the resin composition of the second invention can be within the ranges described above by adjusting the type and content of each component constituting the resin composition.
- the component L which is a soft component with high molecular mobility, can be controlled by the affinity between the resin composition and the filler and the dispersibility of the fillers that inhibit the molecular mobility. Therefore, the relaxation time of the L component can be further shortened by including two or more kinds of carbon black (D) in the resin composition, or by manufacturing by a manufacturing method using dry blending described below.
- thermoplastic resin is not particularly limited, and known thermoplastic resins can be used. Specific examples of thermoplastic resins include polyolefins, polystyrenes, polyacrylates, polymethacrylates, polyacrylonitrile, polyesters, polyamides, polyurethanes, polyethersulfones, polyetherketones, polyimides, polydimethylsiloxanes, polycarbonates, or at least two of these. Seed-containing copolymers, and the like. These thermoplastic resins may be used alone or in combination. It should be noted that the thermoplastic resin is preferably a resin having a high elastic modulus. Polyolefins (olefin-based resins) and polyamides (nylon-based resins) are more preferred, and polyolefins are even more preferred, because they are inexpensive and easy to mold under heat.
- the polyolefin is not particularly limited, and known polyolefins can be used.
- Specific examples of polyolefins include polyethylene, which is an ethylene homopolymer, ethylene- ⁇ -olefin copolymer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid ester copolymer, ethylene-acetic acid.
- Examples include polyethylene resins such as vinyl copolymers.
- the polyolefin is a propylene homopolymer such as polypropylene, a polypropylene-based resin such as a propylene- ⁇ -olefin copolymer, a butene homopolymer such as polybutene, butadiene, or a conjugated diene homopolymer or copolymer such as isoprene. and so on. These polyolefins may be used alone or in combination. From the viewpoint of further increasing the heat resistance and elastic modulus, the polyolefin is preferably polypropylene.
- the polyolefin (olefin resin) preferably contains an ethylene component.
- the content of the ethylene component is preferably 5% by mass to 40% by mass. When the content of the ethylene component is within the above range, it is possible to further improve the heat resistance while further improving the impact resistance of the resin molding.
- the MFR of the thermoplastic resin measured according to JIS K7210 is preferably 10 g/10 min or more, more preferably 30 g/10 min or more, preferably 200 g/10 min or less, more preferably 150 g/10 min or less. be. When the MFR is within the above range, the fluidity of the thermoplastic resin can be further enhanced.
- the content of the thermoplastic resin in the resin composition is preferably 20% by weight or more, more preferably 25% by weight or more, preferably 65% by weight or less, and more preferably 60% by weight or less.
- the content of the thermoplastic resin is within the above range, the moldability of the resin composition can be further enhanced.
- the graphite is not particularly limited, but plate-like graphite is preferable.
- the plate-like graphite is not particularly limited as long as it is plate-like graphite, and for example, graphite, exfoliated graphite, or graphene can be used.
- Graphite or exfoliated graphite is preferred from the viewpoint of further enhancing thermal conductivity and flame retardancy. These may be used alone or in combination.
- scale-like graphite can be used as plate-like graphite. Expanded graphite may be used from the viewpoint of further enhancing flame retardancy.
- Exfoliated graphite is obtained by exfoliating the original graphite, and refers to a graphene sheet laminate that is thinner than the original graphite.
- the exfoliation treatment for exfoliating graphite is not particularly limited, and either a mechanical exfoliation method using a supercritical fluid or the like or a chemical exfoliation method using an acid may be used.
- the number of laminated graphene sheets in exfoliated graphite should be less than that of the original graphite, but is preferably 1000 or less, more preferably 500 or less, and even more preferably 200 or less.
- the volume average particle size of the plate-like graphite is preferably 5 ⁇ m or more, more preferably 30 ⁇ m or more, still more preferably 60 ⁇ m or more, preferably 500 ⁇ m or less, more preferably 350 ⁇ m or less, further preferably 300 ⁇ m or less.
- the volume average particle size of the plate-like graphite is at least the above lower limit, the electromagnetic wave shielding properties and heat dissipation properties can be further enhanced.
- the volume average particle size of the plate-like graphite is equal to or less than the above upper limit, the impact resistance of the resin molded article can be further enhanced.
- the volume average particle size of the plate-like graphite contained in the resin composition of the second invention is within the above range, two or more types of graphite particles having different particle sizes may be used in combination.
- the volume average particle size is a value calculated from a volume standard distribution by a laser diffraction method using a laser diffraction/scattering particle size distribution measuring device in accordance with JIS Z 8825:2013. Say.
- plate-like graphite is put into a soapy water solution (neutral detergent: containing 0.01%) so that its concentration becomes 2% by weight, and ultrasonic waves are applied for 1 minute at an output of 300 W using an ultrasonic homogenizer. , to obtain a suspension.
- the suspension is measured for the volume particle size distribution of the plate-like graphite by a laser diffraction/scattering particle size analyzer (manufactured by Nikkiso Co., Ltd., product name “Microtrac MT3300”).
- the cumulative 50% value of this volume particle size distribution can be calculated as the volume average particle size of the plate-like graphite.
- the content of the plate-like graphite is preferably 50 parts by weight or more, more preferably 70 parts by weight or more, still more preferably 100 parts by weight or more, and preferably 300 parts by weight or less, with respect to 100 parts by weight of the thermoplastic resin. It is preferably 250 parts by weight or less, more preferably 200 parts by weight or less.
- the content of plate-like graphite is at least the above lower limit, the electromagnetic wave shielding properties and heat dissipation properties can be further enhanced.
- the content of plate-like graphite is too large, the area of the interface, which is the starting point of fracture, becomes large. can.
- the aspect ratio of the plate-like graphite is preferably 5 or more, more preferably 21 or more, preferably less than 2000, more preferably less than 1000, still more preferably less than 100.
- the aspect ratio of the plate-like graphite is equal to or higher than the above lower limit, heat dissipation in the planar direction can be further enhanced.
- the aspect ratio of the plate-like graphite is less than the above upper limit, the graphite particles themselves are less likely to bend in the thermoplastic resin during injection molding, for example. Therefore, the electromagnetic wave shielding performance can be further enhanced.
- the aspect ratio refers to the ratio of the maximum dimension of the plate-like graphite in the stacking plane direction to the thickness of the plate-like graphite.
- the thickness of plate-like graphite can be measured using, for example, a transmission electron microscope (TEM) or a scanning electron microscope (SEM). From the viewpoint of making observation easier, a test piece cut out from the resin composition or resin molded body is heated at 600 ° C. to blow off the resin and observed with a transmission electron microscope (TEM) or a scanning electron microscope (SEM). It is desirable to In addition, the test piece may be cut out along the direction along the main surface of the resin molded body as long as the thickness of the plate-like graphite can be measured by skipping the resin, or along the direction perpendicular to the main surface of the resin molded body. You can cut it out.
- TEM transmission electron microscope
- SEM scanning electron microscope
- Carbon black (D) examples of carbon black that can be used include oil furnace black such as ketjen black, acetylene black, channel black, and thermal black. Among them, oil furnace black is preferable from the viewpoint of further increasing the conductivity of the obtained resin molding.
- the ash content of carbon black is preferably 1% or less. Carbon black may also contain metal impurities such as Fe and Ni.
- the BET specific surface area of carbon black is preferably 30 m 2 /g or more, more preferably 50 m 2 /g or more, preferably 2000 m 2 /g or less, more preferably 1500 m 2 /g or less.
- the electrical conductivity can be further improved.
- the BET specific surface area can be measured from the nitrogen adsorption isotherm in accordance with the BET method.
- a measuring device for example, product number "NOVAtouchLX2" manufactured by Anton Paar can be used.
- the DBP oil absorption of carbon black is not particularly limited, but is preferably 50 ml/100 g or more, more preferably 100 ml/100 g or more, preferably 450 ml/100 g or less, more preferably 400 ml/100 g or less.
- the electrical conductivity can be further improved.
- the DBP oil absorption of carbon black can be obtained by calculating the DBP drip amount at 70% of the maximum torque in accordance with JIS K 6217-4.
- the DBP oil absorption can be measured, for example, using an absorption measuring device (manufactured by Asahi Research Institute, product number “S-500”).
- the primary particle size of carbon black is not particularly limited, it is preferably 30 nm or more, more preferably 35 nm or more, preferably 50 nm or less, and more preferably 45 nm or less. When the primary particle size of the carbon black is within the above range, a higher conductivity can be obtained with a lower carbon black content.
- the primary particle size of carbon black is, for example, the average primary particle size obtained using image data of carbon black obtained by a transmission electron microscope.
- a transmission electron microscope for example, the product name "JEM-2200FS” manufactured by JEOL Ltd. can be used.
- the content of carbon black is preferably 3 parts by weight or more, more preferably 5 parts by weight or more, preferably 200 parts by weight or less, and more preferably 150 parts by weight or less with respect to 100 parts by weight of the thermoplastic resin.
- the carbon black content is within the above range, the electrical conductivity and long-term heat resistance can be further enhanced.
- carbon black two or more types may be used as the carbon black.
- the carbon black the first carbon black (C-1) and the second carbon black (C-2) of the first invention may be used.
- the preferable ranges of the content and content ratio are the same as those of the resin composition of the first invention. In this case, the relaxation time of the L component in pulse NMR measurement can be further shortened.
- additives include, for example, phenol-based, phosphorus-based, amine-based, sulfur-based antioxidants; benzotriazole-based, hydroxyphenyltriazine-based UV absorbers; metal damage inhibitors; various fillers; stabilizers; pigments; These may be used alone or in combination.
- the resin composition described above can be obtained by first melt-kneading the thermoplastic resin (A), graphite (B), carbon black (D), and, if necessary, other additives.
- the method of melt-kneading is not particularly limited.
- a method of kneading under the Among these, the method of melt-kneading using an extruder is preferable.
- the form of the resin composition of the second invention is not particularly limited, it can be, for example, a pellet.
- the resin composition of the second invention preferably has a specific volume resistivity of 1.0 ⁇ 10 5 ⁇ cm or less, more preferably 1.0 ⁇ 10 2 ⁇ cm or less.
- the lower limit of the specific volume resistivity is not particularly limited, it is, for example, 1.0 ⁇ 10 ⁇ 4 ⁇ cm.
- the volume specific resistivity can be calculated from the resistivity correction factor and the thickness of the resin composition by measuring the resistance value using a low-resistance resistivity meter. For example, it can be measured at room temperature in the atmosphere using a four-probe resistivity measuring device (Loresta AX MCP-T370, manufactured by Mitsubishi Chemical Analytech).
- first invention and the second invention may be collectively referred to as the present invention.
- each of the first invention and the second invention may be implemented independently, or the first invention and the second invention may be implemented in combination.
- the electromagnetic wave shielding effect of the resin molding at any frequency of 3 GHz, 25 GHz, 50 GHz, and 75 GHz is preferably 20 dB or more. , more preferably 20 dB or more, and still more preferably 41 dB or more.
- the upper limit of the electromagnetic wave shielding effect of the resin molding is not particularly limited, but can be set to 80 dB, for example.
- molten resin composition is filled into the mold from a direction perpendicular to the thickness direction of the resin molding to obtain a resin molding, thereby obtaining a resin molding of 100 mm long ⁇ 100 mm wide ⁇ 2 mm thick.
- the thermal conductivity in the in-plane direction of the resin molding is preferably 1 W/(m K) or more, more preferably 3 W /(m ⁇ K) or more, more preferably 5 W/(m ⁇ K) or more.
- the upper limit of the thermal conductivity in the in-plane direction of the resin molded body can be set to, for example, 50 W/(m ⁇ K).
- the molten resin composition is filled into the mold from the direction orthogonal to the thickness direction of the resin molded body to be obtained, and molded to obtain a resin molded body of length 100 mm ⁇ width 100 mm ⁇ thickness 2 mm.
- a resin molded article according to the present invention is a molded article of the resin composition according to the present invention described above. Therefore, the resin molded article of the present invention can be obtained by molding the resin composition described above.
- the molding method is not particularly limited, but includes, for example, press processing, extrusion processing, extrusion lamination processing, injection molding, and the like. Among them, it is preferable to mold the mixture by injection molding. In this case, the mechanical strength of the resulting resin molding can be further enhanced.
- the resin composition according to the present invention described above is mixed with a composite (E) containing a thermoplastic resin and fibers to obtain a mixture, and then the mixture is molded to obtain a resin molded body. may be obtained.
- the second invention it is desirable to use a mixture of the above resin composition and the composite (E) as the resin composition of the second invention. Therefore, it is desirable to use a mixture of the above resin composition and the above composite for measurement in pulse NMR as well. By using such a mixture, the relaxation time of the L component in pulse NMR measurement can be further shortened.
- the mixture it is preferable to mix the resin composition and the composite (E) by dry blending. In this case, it is possible to obtain a resin molded article with even better mechanical strength.
- dry blending means mixing without melting or adding a solvent.
- the dry blending method is not particularly limited, and for example, it can be performed by simply mixing the resin composition and the composite (E) by hand. Moreover, you may mix using a small tumbler.
- thermoplastic resin contained in the composite (E) the thermoplastic resins described in the resin composition section above can be used.
- the thermoplastic resin contained in the composite (E) is preferably the same resin as the thermoplastic resin contained in the resin composition, but may be a different resin.
- the fibers may be inorganic fibers or organic fibers. Also, inorganic fibers and organic fibers may be used in combination.
- fibers for example, metal fibers, carbon fibers, cellulose fibers, aramid fibers, or glass fibers can be used. These may be used alone or in combination.
- the carbon fiber is not particularly limited, but PAN-based or pitch-based carbon fiber or the like can be used.
- the fibers are preferably oriented in the thermoplastic resin. Among them, it is preferably uniaxially oriented.
- a composite (E) can be produced by aligning fibers and bringing them into contact with a molten thermoplastic resin.
- a composite (E) in which the fibers are impregnated with the thermoplastic resin can be obtained.
- the form of the composite (E) is not particularly limited, but can be, for example, a pellet.
- the length of the fiber is not particularly limited, it is preferably 3 mm or longer, more preferably 5 mm or longer, preferably 20 mm or shorter, and more preferably 15 mm or shorter. When the fiber length is within the above range, the mechanical strength of the obtained resin molding can be further enhanced.
- the fiber diameter of the fibers is preferably 5 ⁇ m or more, more preferably 10 ⁇ m or more, preferably 50 ⁇ m or less, and more preferably 30 ⁇ m or less.
- the mechanical strength of the resulting resin molding can be further enhanced.
- the fiber length and fiber diameter can be, for example, average values of 100 measured using a transmission electron microscope (TEM) or scanning electron microscope (SEM). From the viewpoint of making it easier to observe, a test piece cut out from the composite (E) or the resin molded body is heated at 600 ° C. to remove the resin and a transmission electron microscope (TEM) or a scanning electron microscope (SEM) is used. It is desirable to observe with
- the content of the fiber is not particularly limited, it is preferably 50 parts by weight or more and 200 parts by weight or less with respect to 100 parts by weight of the thermoplastic resin contained in the composite (E).
- the fiber content is within the above range, the mechanical strength of the resulting resin molding can be further enhanced.
- the resin molded article of the present invention can be obtained by the method for producing a resin molded article described above. Since the resin composition of the present invention is used in the method for producing a resin molded product described above, the resin composition is excellent in electrical conductivity and, in turn, in electromagnetic wave shielding properties.
- the resin molding of the present invention preferably has a specific volume resistivity of 1.0 ⁇ 10 5 ⁇ cm or less, more preferably 1.0 ⁇ 10 3 ⁇ cm or less. In this case, the electromagnetic wave shielding property of the resin molding can be further enhanced.
- the lower limit of the specific volume resistivity is not particularly limited, it can be, for example, 1.0 ⁇ 10 ⁇ 4 ⁇ cm.
- the specific volume resistivity can be calculated from the resistivity correction coefficient and the thickness of the resin molding by measuring the resistance value using a low-resistance resistivity meter. For example, it can be measured at room temperature in the atmosphere using a four-probe resistivity measuring device (Loresta AX MCP-T370, manufactured by Mitsubishi Chemical Analytech).
- the resin molding of the present invention has an electromagnetic wave shielding effect of preferably 20 dB or more, more preferably 25 dB or more, and still more preferably 30 dB or more at a frequency of 3 GHz.
- the upper limit of the electromagnetic wave shielding effect is not particularly limited, but is, for example, 80 dB.
- the electromagnetic wave shielding effect (electromagnetic wave shielding performance) at a frequency of 3 GHz can be measured using, for example, the Dual-Focus Flat Cavity (DFFC) method.
- DFFC Dual-Focus Flat Cavity
- the in-plane thermal conductivity of the main surface of the resin molded body is preferably 2 W/(m K) or more, more preferably 5 W/(m K) or more, and still more preferably 10 W/(m ⁇ K) or more.
- the heat dissipation of the resin molding can be further enhanced.
- the upper limit value of the thermal conductivity in the in-plane direction is not particularly limited, it can be set to, for example, 50 W/(m ⁇ K).
- the main surface may be a flat surface or a curved surface.
- the main surface means a surface having the largest area among a plurality of surfaces on the outer surface of the resin molding, and means a continuous surface.
- the thermal conductivity in the in-plane direction can be calculated using the following formula (1).
- the thermal diffusivity can be measured, for example, using Netsch Japan's product number "Xenon Flash Laser Analyzer LFA467 HyperFlash”.
- the resin molded product of the present invention has excellent electromagnetic shielding properties, it can be suitably used for housings of electronic equipment such as communication devices requiring electromagnetic shielding properties, smart meters, and in-vehicle ECUs.
- the resin molding of the present invention may be in the shape of a heat dissipation chassis, a heat dissipation housing, or a heat sink. Specific examples of the shape of the heat dissipation chassis, the heat dissipation housing, and the heat sink will be described below with reference to FIGS. 1 to 3.
- FIG. 1 Specific examples of the shape of the heat dissipation chassis, the heat dissipation housing, and the heat sink will be described below with reference to FIGS. 1 to 3.
- FIG. 1 is a schematic perspective view of a heat dissipation chassis.
- the resin molded body is a heat radiating chassis, the main surface is the portion indicated by arrow A in FIG.
- FIG. 2 is a schematic perspective view of the heat dissipation housing.
- the portion indicated by arrow B in FIG. 2 is the main surface.
- the main surface may have unevenness
- FIG. 3 is a schematic perspective view of a heat sink shape.
- the portion indicated by arrow C in FIG. 3 is the main surface.
- the main surface on one side of the bottom plate portion and the surface of the fin portion are the main surfaces.
- multiple principal surfaces may exist.
- a circuit may be formed on the surface of such a resin molding.
- Example 1 100 parts by weight of polypropylene (PP) as a thermoplastic resin, 150 parts by weight of scaly graphite particles as plate-like graphite particles, 20 parts by weight of oil furnace black as the first carbon black, and the second carbon black and 20 parts by weight of oil furnace black as are melt-kneaded at 200° C. using Laboplastomill (manufactured by Toyo Seiki Co., Ltd., product number “R100”) to obtain a resin composition.
- the obtained resin composition was injection-molded at a resin composition temperature of 230° C. and a mold temperature of 40° C. to obtain a resin molded body of length 300 mm ⁇ width 300 mm ⁇ thickness 2 mm.
- polypropylene trade name "BC08F” (MFR: 70 g/10 min (230°C)) manufactured by Japan Polypropylene Corporation was used.
- scale-like graphite particles trade name “CPB-100B” (volume average particle diameter: 80 ⁇ m) manufactured by Chuetsu Graphite Co., Ltd. was used.
- oil furnace black of the first carbon black Lion Corporation's product name "EC300J” (BET specific surface area: 800 m 2 /g, DBP oil absorption: 365 ml/100 g, primary particle diameter: 40 nm) was used.
- the MFR of the thermoplastic resins in Examples and Comparative Examples was measured according to JIS K7210.
- the volume-average particle size of graphite is determined according to JIS Z 8825: 2013, using a laser diffraction/scattering particle size distribution measuring device (manufactured by Nikkiso Co., Ltd., product name "Microtrac MT3300"), using a laser diffraction method. Calculated by distribution.
- the BET specific surface areas of the first and second carbon blacks were measured from nitrogen adsorption isotherms according to the BET method.
- Anton Paar's product number "NOVAtouchLX2" was used as a measuring device.
- the DBP oil absorption of the first and second carbon blacks was measured using an absorption measuring instrument (manufactured by Asahi Research Institute, product number "S-500"), and the maximum torque of 70% was measured in accordance with JIS K 6217-4. It was obtained by calculating the DBP dropping amount in %.
- the primary particle sizes of the first and second carbon blacks were determined from the average value of 1000 carbon blacks in the image data obtained by a transmission electron microscope (manufactured by JEOL Ltd., product name "JEM-2200FS”). .
- Example 2 The oil furnace black as the first carbon black was changed to Lionite CB (product name: BET specific surface area: 1052 m 2 /g, DBP oil absorption: 280 ml/100 g, primary particle diameter: 41 nm) manufactured by Lion Corporation.
- a resin composition and a resin molding were obtained in the same manner as in Example 1 except for the above.
- Example 3 Except for changing the oil furnace black as the first carbon black to Cabot's trade name "BlackPearls 2000" (BET specific surface area: 1475 m 2 /g, DBP oil absorption: 330 ml/100 g, primary particle size: 15 nm). obtained a resin composition and a resin molding in the same manner as in Example 1.
- Example 4 The oil furnace black as the second carbon black was changed to "F-200GS" (BET specific surface area: 55 m 2 /g, DBP oil absorption: 55 ml/100 g, primary particle diameter: 38 nm) manufactured by Asahi Carbon Co., Ltd. A resin composition and a resin molding were obtained in the same manner as in Example 1, except that the above was performed.
- F-200GS BET specific surface area: 55 m 2 /g, DBP oil absorption: 55 ml/100 g, primary particle diameter: 38 nm
- Example 5 In the same manner as in Example 1, except that the scale-like graphite particles as the plate-like graphite particles were changed to "CPB-300" (volume average particle size: 300 ⁇ m) manufactured by Chuetsu Graphite Co., Ltd. A resin composition and a resin molding were obtained.
- CB-300 volume average particle size: 300 ⁇ m
- Example 6 A resin A composition and a resin molding were obtained.
- Example 7 A resin composition was prepared in the same manner as in Example 1, except that polypropylene (PP) as a thermoplastic resin was changed to Japan Polypropylene Co., Ltd., trade name "SA06GA” (MFR: 60 g / 10 min (230 ° C.)). and a resin molding was obtained.
- PP polypropylene
- SA06GA trade name
- Example 8 The thermoplastic resin was changed to 6 nylon manufactured by Toray Industries, trade name "CM1007" (MFR: 62 g / 10 min (260 ° C.)), the melt kneading temperature was 230 ° C., and the injection molding temperature was 260 ° C. , in the same manner as in Example 1, to obtain a resin composition and a resin molding.
- CM1007 MFR: 62 g / 10 min (260 ° C.)
- Example 9 Production of resin composition (A-1); 100 parts by weight of polypropylene (PP) as a thermoplastic resin, 160 parts by weight of flake graphite as plate-like graphite, 20 parts by weight of oil furnace black as the first carbon black, and oil as the second carbon black 20 parts by weight of furnace black was used. These were melt-kneaded at 200° C. using Laboplastomill (manufactured by Toyo Seiki Co., Ltd., product number “R100”) to obtain a resin composition (A-1).
- PP polypropylene
- flake graphite as plate-like graphite
- oil furnace black oil as the second carbon black 20 parts by weight of furnace black
- the obtained resin composition (A-1) was in the form of pellets with a pellet diameter of 3 mm.
- the pellet diameter was determined by randomly extracting 100 pellets from the sample and measuring the diameter at the longest point using a vernier caliper.
- trade name "MA04A” MFR: 40 g/10 minutes (230°C)
- flake graphite trade name “CPB-300” (average particle size: 300 ⁇ m, aspect ratio: 10) manufactured by Chuetsu Graphite Co., Ltd. was used.
- resin composition (B-1) Using 60 parts by weight of polypropylene (PP) as a thermoplastic resin and 40 parts by weight of glass fiber having a length of 7 mm, a resin composition (B-1) was obtained according to the pultrusion method. The obtained resin composition (B-1) was in the form of pellets with a pellet diameter of 7 mm. Also, as the polypropylene, trade name “MA04A” (MFR: 40 g/10 min (230° C.)) manufactured by Japan Polypropylene Corporation was used. As the roving fiber (glass fiber), trade name "TUFROV4520" (fiber diameter: 16 ⁇ m) manufactured by Nippon Electric Glass Co., Ltd. was used.
- TUFROV4520 fiber diameter: 16 ⁇ m
- the obtained resin composition (A-1) and resin composition (B-1) were dry-blended at a ratio of 85:15 using a small tumbler at a rotation speed of 30 rpm for 5 minutes to obtain a resin composition. got stuff Otherwise, the resin molding was obtained in the same manner as in Example 1.
- Example 1 A resin composition and a resin molding were obtained in the same manner as in Example 1, except that the content of the plate-like graphite particles was changed to 200 parts by weight and the first and second carbon blacks were not used. rice field.
- Comparative example 2 A resin composition and a resin molding were obtained in the same manner as in Example 1, except that the content of the first carbon black was changed to 40 parts by weight and the second carbon black was not used.
- Example 3 A resin composition and a resin molding were obtained in the same manner as in Example 1, except that the content of the second carbon black was changed to 40 parts by weight and the first carbon black was not used.
- the electromagnetic shielding effect (electromagnetic shielding performance, unit: dB) of the resin moldings obtained in Examples 1 to 9 and Comparative Examples 1 to 3 at a frequency of 3 GHz was measured using a jig for measuring shield characteristics.
- Flat Cavity: DFFC (manufactured by Sanken Co., Ltd.) was used for measurement.
- an electromagnetic wave was emitted from the focal point on the transmitting side, and the intensity of the electromagnetic wave converged on the focal point on the receiving side was measured as the received voltage.
- the received voltage V0 when the sample was not inserted and the received voltage V when the sample was inserted were measured, and the electromagnetic wave shielding effect was calculated according to the following equation ( 2 ).
- Electromagnetic wave shielding effect 20 ⁇ log 10 (V 0 /V) Equation (2)
- the measurement frequency range was 1 GHz to 15 GHz, and the measuring instrument used was Agilent Technologies' part number "Component Analyzer N4375D".
- the sample size of the resin molding was 300 mm ⁇ 20 mm ⁇ 2.0 mm.
- Example 10 Instead of the first carbon black and the second carbon black, oil furnace black as carbon black (manufactured by Lion Corporation, trade name “Lionite CB”, BET specific surface area: 1052 m 2 /g, DBP oil absorption: 280 ml / 100 g, primary particle diameter: 41 nm) 40 parts by weight was used. Otherwise, the resin composition was obtained in the same manner as in Example 9.
- oil furnace black as carbon black (manufactured by Lion Corporation, trade name “Lionite CB”, BET specific surface area: 1052 m 2 /g, DBP oil absorption: 280 ml / 100 g, primary particle diameter: 41 nm) 40 parts by weight was used. Otherwise, the resin composition was obtained in the same manner as in Example 9.
- Example 11 100 parts by weight of polypropylene (PP) as a thermoplastic resin, 160 parts by weight of scaly graphite as plate-like graphite particles, and 40 parts by weight of oil furnace black as carbon black were mixed together in Lab Plastomill (manufactured by Toyo Seiki Co., Ltd.). , product number "R100”) was melt-kneaded at 200°C to obtain a resin composition.
- PP polypropylene
- MA04A MFR: 40 g/10 min (230°C)
- flake graphite trade name “CPB-300” (average particle size: 300 ⁇ m, aspect ratio: 10) manufactured by Chuetsu Graphite Co., Ltd. was used.
- CB-300 average particle size: 300 ⁇ m, aspect ratio: 10
- Lionite CB trade name manufactured by Lion Corporation (BET specific surface area: 1052 m 2 /g, DBP oil absorption: 280 ml/100 g, primary particle diameter: 41 nm) was used.
- Example 12 Production of resin composition (A-2); 100 parts by weight of polypropylene (PP) as a thermoplastic resin, 70 parts by weight of flake graphite as plate-like graphite, and 30 parts by weight of oil furnace black as carbon black were used. These were melt-kneaded at 200° C. using Laboplastomill (manufactured by Toyo Seiki Co., Ltd., product number “R100”) to obtain a resin composition (A-2).
- PP polypropylene
- flake graphite as plate-like graphite
- oil furnace black oil furnace black
- the obtained resin composition (A-2) was in the form of pellets with a pellet diameter of 3 mm.
- the pellet diameter was determined by randomly extracting 100 pellets from the sample and measuring the diameter at the longest point using a vernier caliper.
- trade name "MA04A” MFR: 40 g/10 minutes (230°C)
- flake graphite trade name “CPB-300” (average particle size: 300 ⁇ m, aspect ratio: 10) manufactured by Chuetsu Graphite Co., Ltd. was used.
- the obtained resin composition (A-2) and the same resin composition (B-1) as in Example 9 are dry blended at a ratio of 70:30 using a small tumbler at a rotation speed of 30 rpm for 5 minutes. Thus, a resin composition was obtained.
- the resin compositions obtained in Examples 4, 9 to 12 and Comparative Example 1 were injection molded to obtain resin moldings of length 100 mm, width 100 mm, and thickness 2 mm. Also. A sample of the resin molding was obtained by cutting the obtained flat plate of the resin molding into a 5 mm square. Injection molding was performed under the conditions of a resin temperature of 230° C., a mold temperature of 50° C., and an injection speed of 30 mm/s.
- 700 mg of a sample of the obtained resin molding was introduced into a glass sample tube having a diameter of 10 mm (manufactured by BRUKER, product number 1824511, diameter of 10 mm, length of 180 mm, flat bottom). Then, the sample tube was placed in a pulse NMR device ("the minispe mq20" manufactured by BRUKER) and held at 125°C for 10 minutes. After that, the Hahn Echo method was performed at 125° C., and the obtained 1 H spin-spin relaxation free induction decay curve was divided into three components, the S component, the M component, and the L component, in the order of shortest relaxation time by the least-squares method. The waveforms were separated into three curves derived from each.
- Waveform separation was performed by fitting using the exponential type. Fitting was performed using analysis software "TD-NMRA (Version 4.3 Rev 0.8)" manufactured by BRUKER according to the product manual.
- w1 to w3 are Weibull coefficients, and w1, w2 and w3 take the value of 1.
- A1 is the S component
- B1 is the M component
- C1 is the component ratio of the L component
- T2A is the relaxation time of the S component
- T2B is the M component
- T2C is the L component.
- t is time.
- the resin compositions obtained in Examples 4 and 9 to 12 and Comparative Example 1 were injection-molded to obtain resin moldings of length 100 mm, width 100 mm, and thickness 2 mm, which were used as measurement samples. Injection molding was performed under the conditions of a resin temperature of 230° C., a mold temperature of 50° C., and an injection speed of 30 mm/s.
- the electromagnetic wave shielding effect (electromagnetic wave shielding performance, unit: dB) of the obtained resin molding at a frequency of 3 GHz was measured using a jig for measuring shield characteristics, Dual-Focus Flat Cavity (DFFC) (manufactured by Sanken Co., Ltd.). measured by Specifically, an electromagnetic wave was emitted from the focal point on the transmitting side, and the intensity of the electromagnetic wave converged on the focal point on the receiving side was measured as the received voltage. The received voltage V0 when the sample was not inserted and the received voltage V when the sample was inserted were measured, and the electromagnetic wave shielding effect was calculated according to the following equation ( 2 ).
- DFFC Dual-Focus Flat Cavity
- Electromagnetic wave shielding effect 20 ⁇ log 10 (V 0 /V) Equation (2)
- the measurement frequency range was 1 GHz to 15 GHz, and the measuring instrument used was Agilent Technologies' part number "Component Analyzer N4375D".
- the sample size of the resin molding was 100 mm ⁇ 100 mm ⁇ 2 mm.
- the thermal conductivity (in-plane direction and thickness direction thermal conductivity) of the obtained measurement sample was measured using Netch Japan's product number "Xenon Flash Laser Analyzer LFA467 HyperFlash”. Specifically, the measurement sample was fitted into a holder in a direction that allows the thermal conductivity to be measured, the thermal diffusivity at 30° C. was measured, and the thermal conductivity was calculated according to the following formula (1).
- test pieces were exposed to constant temperature baths at 23 ° C. and 125 ° C. for 3000 hours each, and the test pieces left in the 23 ° C. atmosphere were treated as before heat deterioration, and the test pieces left in the 125 ° C. atmosphere were treated as heat deterioration. It was used as a measurement sample later.
- a tensile test was performed in accordance with ISO 527 to measure the tensile strength. Long-term heat resistance was calculated according to the following formula (2).
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Abstract
Description
本願の第1の発明の樹脂組成物は、熱可塑性樹脂(A)と、黒鉛(B)と、2種以上のカーボンブラック(C)とを含む。上記カーボンブラック(C)は、BET比表面積が600m2/g以上の第1のカーボンブラック(C-1)と、BET比表面積が600m2/g未満の第2のカーボンブラック(C-2)とを含有する。
熱可塑性樹脂としては、特に限定されず、公知の熱可塑性樹脂を用いることができる。熱可塑性樹脂の具体例としては、ポリオレフィン、ポリスチレン、ポリアクリレート、ポリメタクリレート、ポリアクリロニトリル、ポリエステル、ポリアミド、ポリウレタン、ポリエーテルスルホン、ポリエーテルケトン、ポリイミド、ポリジメチルシロキサン、ポリカーボネート、又はこれらのうち少なくとも2種を含む共重合体などが挙げられる。これらの熱可塑性樹脂は、単独で用いてもよく、複数を併用してもよい。なお、熱可塑性樹脂としては、弾性率の高い樹脂であることが好ましい。安価であり、加熱下での成形が容易であることから、ポリオレフィン(オレフィン系樹脂)及びポリアミド(ナイロン系樹脂)がより好ましい。
黒鉛としては、特に限定されないが、板状黒鉛であることが好ましい。板状黒鉛としては、板状の黒鉛である限りにおいて特に限定されないが、例えば、黒鉛、薄片化黒鉛、又はグラフェンなどを用いることができる。熱伝導性及び難燃性をより一層高める観点から、好ましくは黒鉛又は薄片化黒鉛である。これらは、単独で用いてもよく、複数を併用してもよい。なお、第1の発明において、板状黒鉛としては、例えば、鱗片状黒鉛を用いることができる。難燃性をより一層高める観点から、膨張黒鉛であってもよい。
第1のカーボンブラック(C-1);
第1のカーボンブラックとしては、例えば、ケッチェンブラックなどのオイルファーネスブラック、アセチレンブラック、チャンネルブラック、サーマルブラックなどを用いることができる。なかでも、得られる樹脂成形体の導電性をより一層高める観点から、オイルファーネスブラックであることが好ましい。なお、カーボンブラックの灰分は、1%以下であることが好ましい。また、カーボンブラックは、Fe、Niなどの金属不純物を含有していてもよい。
第2のカーボンブラックとしては、例えば、ケッチェンブラックなどのオイルファーネスブラック、アセチレンブラック、チャンネルブラック、サーマルブラックなどを用いることができる。なかでも、得られる樹脂成形体の導電性をより一層高める観点から、オイルファーネスブラックであることが好ましい。特に、第1のカーボンブラック及び第2のカーボンブラックの双方が、オイルファーネスブラックであることがより好ましい。なお、カーボンブラックの灰分は、1%以下であることが好ましい。また、カーボンブラックは、Fe、Niなどの金属不純物を含有していてもよい。
第1の発明の樹脂組成物には、第1の発明の効果を阻害しない範囲において、任意成分として様々なその他添加剤が添加されていてもよい。添加剤としては、例えば、フェノール系、リン系、アミン系、イオウ系などの酸化防止剤;ベンゾトリアゾール系、ヒドロキシフェニルトリアジン系などの紫外線吸収剤;金属害防止剤;各種充填剤;帯電防止剤;安定剤;顔料などが挙げられる。これらは、単独で用いてもよく、複数を併用してもよい。
上述した樹脂組成物は、まず、熱可塑性樹脂(A)と、黒鉛(B)と、BET比表面積が600m2/g以上の第1のカーボンブラック(C-1)と、BET比表面積が600m2/g未満の第2のカーボンブラック(C-2)と、必要に応じてその他添加剤とを溶融混錬することにより得ることができる。
本願の第2の発明の樹脂組成物は、熱可塑性樹脂(A)と、黒鉛(B)と、カーボンブラック(D)とを含む。また、第2の発明の樹脂組成物は、パルスNMRを用いて以下の測定をしたときに、L成分の緩和時間が1.3msec以下である。
金型内に溶融状態の上記第2の発明の樹脂組成物を得られる樹脂成形体の厚み方向に直交する方向から充填させて成形し、縦100mm×横100mm×厚み2mmの樹脂成形体を得る。得られた樹脂成形体の平板を5mm角にカットすることで樹脂成形体のサンプルを得る。
Scans:16times
Recycle Deray:1sec
First 90-180 Pluse Separation:0.0082msec
Final Pluse Separation:5msec
Number of Points for Fitting:100
熱可塑性樹脂としては、特に限定されず、公知の熱可塑性樹脂を用いることができる。熱可塑性樹脂の具体例としては、ポリオレフィン、ポリスチレン、ポリアクリレート、ポリメタクリレート、ポリアクリロニトリル、ポリエステル、ポリアミド、ポリウレタン、ポリエーテルスルホン、ポリエーテルケトン、ポリイミド、ポリジメチルシロキサン、ポリカーボネート、又はこれらのうち少なくとも2種を含む共重合体などが挙げられる。これらの熱可塑性樹脂は、単独で用いてもよく、複数を併用してもよい。なお、熱可塑性樹脂としては、弾性率の高い樹脂であることが好ましい。安価であり、加熱下での成形が容易であることから、ポリオレフィン(オレフィン系樹脂)及びポリアミド(ナイロン系樹脂)がより好ましく、ポリオレフィンがさらに好ましい。
黒鉛としては、特に限定されないが、板状黒鉛であることが好ましい。板状黒鉛としては、板状の黒鉛である限りにおいて特に限定されないが、例えば、黒鉛、薄片化黒鉛、又はグラフェンなどを用いることができる。熱伝導性及び難燃性をより一層高める観点から、好ましくは黒鉛又は薄片化黒鉛である。これらは、単独で用いてもよく、複数を併用してもよい。なお、第2の発明において、板状黒鉛としては、例えば、鱗片状黒鉛を用いることができる。難燃性をより一層高める観点から、膨張黒鉛であってもよい。
カーボンブラックとしては、例えば、ケッチェンブラックなどのオイルファーネスブラック、アセチレンブラック、チャンネルブラック、サーマルブラックなどを用いることができる。なかでも、得られる樹脂成形体の導電性をより一層高める観点から、オイルファーネスブラックであることが好ましい。なお、カーボンブラックの灰分は、1%以下であることが好ましい。また、カーボンブラックは、Fe、Niなどの金属不純物を含有していてもよい。
第2の発明の樹脂組成物には、第2の発明の効果を阻害しない範囲において、任意成分として様々なその他添加剤が添加されていてもよい。添加剤としては、例えば、フェノール系、リン系、アミン系、イオウ系などの酸化防止剤;ベンゾトリアゾール系、ヒドロキシフェニルトリアジン系などの紫外線吸収剤;金属害防止剤;各種充填剤;帯電防止剤;安定剤;顔料などが挙げられる。これらは、単独で用いてもよく、複数を併用してもよい。
上述した樹脂組成物は、まず、熱可塑性樹脂(A)と、黒鉛(B)と、カーボンブラック(D)と、必要に応じてその他添加剤とを溶融混錬することにより得ることができる。
金型内に溶融状態の樹脂組成物を得られる樹脂成形体の厚み方向に直交する方向から充填させて成形し、縦100mm×横100mm×厚み2mmの樹脂成形体を得る。
金型内に溶融状態の樹脂組成物を得られる樹脂成形体の厚み方向に直交する方向から充填させて成形し、縦100mm×横100mm×厚み2mmの樹脂成形体を得る。
本発明に係る樹脂成形体は、上述した本発明に係る樹脂組成物の成形体である。従って、本発明の樹脂成形体は、上述した樹脂組成物を成形することにより得ることができる。
本発明の樹脂成形体は、上述した樹脂成形体の製造方法により得ることができる。上述した樹脂成形体の製造方法では、本発明の樹脂組成物を用いているので、導電性に優れ、ひいては電磁波シールド性に優れている。
熱可塑性樹脂としてのポリプロピレン(PP)100重量部と、板状の黒鉛粒子としての鱗片状黒鉛粒子150重量部と、第1のカーボンブラックとしてのオイルファーネスブラック20重量部と、第2のカーボンブラックとしてのオイルファーネスブラック20重量部とを、ラボプラストミル(東洋精機社製、品番「R100」)を用いて、200℃で溶融混練することにより樹脂組成物を得た。得られた樹脂組成物を、樹脂組成物の温度230℃、金型の温度40℃にて射出成形することで、縦300mm×横300mm×厚み2mmの樹脂成形体を得た。なお、ポリプロピレンとしては、日本ポリプロ社製、商品名「BC08F」(MFR:70g/10min(230℃))を用いた。鱗片状黒鉛粒子としては、中越黒鉛工業所社製、商品名「CPB-100B」(体積平均粒子径:80μm)を用いた。第1のカーボンブラックのオイルファーネスブラックとしては、ライオン社製、商品名「EC300J」(BET比表面積:800m2/g、DBP吸油量:365ml/100g、一次粒子径:40nm)を用いた。第2のカーボンブラックのオイルファーネスブラックとしては、キャボット社製、商品名「VulcanXC72」(BET比表面積:254m2/g、DBP吸油量:174ml/100g、一次粒子径:30nm)を用いた。
第1のカーボンブラックとしてのオイルファーネスブラックを、ライオン社製、商品名「ライオナイトCB」(BET比表面積:1052m2/g、DBP吸油量:280ml/100g、一次粒子径:41nm)に変更したこと以外は、実施例1と同様にして、樹脂組成物及び樹脂成形体を得た。
第1のカーボンブラックとしてのオイルファーネスブラックを、キャボット社製、商品名「BlackPearls2000」(BET比表面積:1475m2/g、DBP吸油量:330ml/100g、一次粒子径:15nm)に変更したこと以外は、実施例1と同様にして、樹脂組成物及び樹脂成形体を得た。
第2のカーボンブラックとしてのオイルファーネスブラックを、旭カーボン社製、商品名「F-200GS」(BET比表面積:55m2/g、DBP吸油量:55ml/100g、一次粒子径:38nm)に変更したこと以外は、実施例1と同様にして、樹脂組成物及び樹脂成形体を得た。
板状の黒鉛粒子としての鱗片状黒鉛粒子を、中越黒鉛工業所社製、商品名「CPB-300」(体積平均粒子径:300μm)に変更したこと以外は、実施例1と同様にして、樹脂組成物及び樹脂成形体を得た。
板状の黒鉛粒子としての鱗片状黒鉛粒子を、日本黒鉛工業社製、商品名「F#2」(体積平均粒子径:140μm)に変更したこと以外は、実施例1と同様にして、樹脂組成物及び樹脂成形体を得た。
熱可塑性樹脂としてのポリプロピレン(PP)を、日本ポリプロ社製、商品名「SA06GA」(MFR:60g/10min(230℃))に変更したこと以外は、実施例1と同様にして、樹脂組成物及び樹脂成形体を得た。
熱可塑性樹脂を、東レ社製、6ナイロン、商品名「CM1007」(MFR:62g/10min(260℃))に変更し、溶融混練温度を230℃、射出成形温度を260℃としたこと以外は、実施例1と同様にして、樹脂組成物及び樹脂成形体を得た。
樹脂組成物(A-1)の製造;
熱可塑性樹脂としてのポリプロピレン(PP)100重量部と、板状黒鉛としての鱗片状黒鉛160重量部と、第1のカーボンブラックとしてのオイルファーネスブラック20重量部と、第2のカーボンブラックとしてのオイルファーネスブラック20重量部とを用いた。これらをラボプラストミル(東洋精機社製、品番「R100」)を用いて、200℃で溶融混練することにより樹脂組成物(A-1)を得た。
熱可塑性樹脂としてのポリプロピレン(PP)60重量部と、長さ7mmのガラス繊維40重量部とを用い、プルトルージョン法に従い樹脂組成物(B-1)を得た。なお、得られた樹脂組成物(B-1)は、ペレット状であり、ペレット径は、7mmであった。また、ポリプロピレンとしては、日本ポリプロ社製、商品名「MA04A」(MFR:40g/10分(230℃))を用いた。ロービング繊維(ガラス繊維)としては、日本電気硝子社製、商品名「TUFROV4520」(繊維径:16μm)を用いた。
板状の黒鉛粒子の含有量を200重量部に変更し、第1及び第2のカーボンブラックを使用しなかったこと以外は、実施例1と同様にして、樹脂組成物及び樹脂成形体を得た。
第1のカーボンブラックの含有量を40重量部に変更し、第2のカーボンブラックを使用しなかったこと以外は、実施例1と同様にして、樹脂組成物及び樹脂成形体を得た。
第2のカーボンブラックの含有量を40重量部に変更し、第1のカーボンブラックを使用しなかったこと以外は、実施例1と同様にして、樹脂組成物及び樹脂成形体を得た。
<体積抵抗率>
実施例1~9及び比較例1~3で得られた樹脂成形体の体積抵抗率は、四探針法抵抗率測定装置(三菱ケミカルアナリテック社製、品番「ロレスタAX MCP-T370」)を用いて測定した。
実施例1~9及び比較例1~3で得られた樹脂成形体の周波数3GHzにおける電磁波シールド効果(電磁波遮蔽性能、単位:dB)は、シールド特性測定用冶具2焦点型扁平空洞(Dual-Focus Flat Cavity:DFFC)(サンケン社製)を用いて測定した。具体的には、送信側の焦点から電磁波を放射し、受信側の焦点に収束した電磁波の強度を受信電圧として測定した。サンプル未挿入時の受信電圧V0及びサンプル挿入時の受信電圧Vを測定し、以下の式(2)に従って電磁波シールド効果を算出した。
実施例1~9及び比較例1~3で得られた樹脂組成物の流動性はスパイラルフロー流動長として評価した。具体的には、幅20mm×厚さ2mmのアルキメデス螺旋スパイラル状の流路を持つ樹脂流動長測定用金型を用いて、シリンダー温度230℃、金型温度40℃、射出圧力150MPaにて射出成形を行ったときの流動長を測定した。
第1のカーボンブラック及び第2のカーボンブラックの代わりに、カーボンブラックとしてのオイルファーネスブラック(ライオン社製、商品名「ライオナイトCB」、BET比表面積:1052m2/g、DBP吸油量:280ml/100g、一次粒子径:41nm)40重量部を用いた。その他の点は、実施例9と同様にして樹脂組成物を得た。
熱可塑性樹脂としてのポリプロピレン(PP)100重量部と、板状の黒鉛粒子としての鱗片状黒鉛160重量部と、カーボンブラックとしてのオイルファーネスブラック40重量部とを、ラボプラストミル(東洋精機社製、品番「R100」)を用いて、200℃で溶融混練することにより樹脂組成物を得た。なお、ポリプロピレンとしては、日本ポリプロ社製、商品名「MA04A」(MFR:40g/10min(230℃))を用いた。鱗片状黒鉛としては、中越黒鉛工業所社製、商品名「CPB-300」(平均粒子径:300μm、アスペクト比:10)を用いた。オイルファーネスブラックとしては、ライオン社製、商品名「ライオナイトCB」(BET比表面積:1052m2/g、DBP吸油量:280ml/100g、一次粒子径:41nm)を用いた。
樹脂組成物(A-2)の製造;
熱可塑性樹脂としてのポリプロピレン(PP)100重量部と、板状黒鉛としての鱗片状黒鉛70重量部と、カーボンブラックとしてのオイルファーネスブラック30重量部とを用いた。これらをラボプラストミル(東洋精機社製、品番「R100」)を用いて、200℃で溶融混練することにより樹脂組成物(A-2)を得た。
(パルスNMR)
実施例4,9~12及び比較例1で得られた樹脂組成物について、パルスNMRを用いて125℃でHahn Echo法を行い、得られた1Hのスピン-スピン緩和の自由誘導減衰曲線を、最小二乗法により緩和時間の短い順にS成分、M成分、L成分の3成分にそれぞれ由来する3つの曲線に波形分離した。そして、L成分の緩和時間、並びにS成分、M成分、及びL成分の合計に対するL成分の比(L成分/(S成分+M成分+L成分))を算出し、以下の評価基準で評価した。
L成分の緩和時間;
〇…1.3msec以下
×…1.3msecを超える
〇…10%以下
×…10%を超える
〇…4%以上
×…4%未満
Recycle Deray:1sec
First 90-180 Pluse Separation:0.0082msec
Final Pluse Separation:5msec
Number of Points for Fitting:100
実施例4,9~12及び比較例1で得られた樹脂組成物を射出成形し、縦100mm×横100mm×厚み2mmの樹脂成形体を得て、測定サンプルとした。なお、射出成形は、樹脂温度230℃、金型温度50℃、射出速度30mm/sの条件で行った。
実施例4,9~12及び比較例1で得られた樹脂組成物を射出成形し、縦100mm×横100mm×厚み2mmの樹脂成形体を得て、測定サンプルとした。なお、射出成形は、樹脂温度230℃、金型温度50℃、射出速度30mm/sの条件で行った。
実施例4,9~12及び比較例1で得られた樹脂組成物を射出成形し、ISO 527に準拠したダンベル形状の試験片を得た。なお、射出成形は、樹脂温度230℃、金型温度50℃、射出速度30mm/sの条件で行った。
Claims (20)
- 熱可塑性樹脂(A)と、黒鉛(B)と、2種以上のカーボンブラック(C)とを含み、
前記カーボンブラック(C)は、BET比表面積が600m2/g以上の第1のカーボンブラック(C-1)と、BET比表面積が600m2/g未満の第2のカーボンブラック(C-2)とを含有する、樹脂組成物。 - 前記熱可塑性樹脂(A)100重量部に対し、
前記第1のカーボンブラック(C-1)の含有量が、5重量部以上、50重量部以下であり、
前記第2のカーボンブラック(C-2)の含有量が、5重量部以上、50重量部以下であり、
前記カーボンブラック(C)全体の含有量が、15重量部以上、90重量部以下である、請求項1に記載の樹脂組成物。 - 前記第1のカーボンブラック(C-1)のDBP吸油量が、250ml/100g以上であり、
前記第2のカーボンブラック(C-2)のDBP吸油量が、250ml/100g未満である、請求項1又は2に記載の樹脂組成物。 - 前記カーボンブラック(C)の灰分が、1%以下である、請求項1~3のいずれか1項に1項に記載の樹脂組成物。
- 前記黒鉛(B)が、板状黒鉛である、請求項1~4のいずれか1項に記載の樹脂組成物。
- 前記黒鉛(B)の体積平均粒子径が、5μm以上、500μm以下である、請求項1~5のいずれか1項に記載の樹脂組成物。
- 前記熱可塑性樹脂(A)100重量部に対し、前記黒鉛(B)の含有量が、50重量部以上、300重量部以下である、請求項1~6のいずれか1項に記載の樹脂組成物。
- 前記熱可塑性樹脂(A)が、オレフィン系樹脂及びナイロン系樹脂のうち、少なくとも一方の樹脂である、請求項1~7のいずれか1項に記載の樹脂組成物。
- 体積固有抵抗率が1.0×105Ω・cm以下である、請求項1~8のいずれか1項に記載の樹脂組成物。
- 熱可塑性樹脂(A)と、黒鉛(B)と、カーボンブラック(D)とを含む、樹脂組成物であって、
金型内に溶融状態の前記樹脂組成物を得られる樹脂成形体の厚み方向に直交する方向から充填させて成形し、縦100mm×横100mm×厚み2mmの樹脂成形体を得たときに、
パルスNMRを用いて125℃でHahn Echo法により前記樹脂成形体を測定することによって得られる1Hのスピン-スピン緩和の自由誘導減衰曲線を、最小二乗法により緩和時間の短い順にS成分、M成分、及びL成分の3成分にそれぞれ由来する3つの曲線に波形分離したときに、前記L成分の緩和時間が1.3msec以下である、樹脂組成物。 - 前記S成分、前記M成分、及び前記L成分の合計に対する前記L成分の比(L成分/(S成分+M成分+L成分))が10%以下である、請求項10に記載の樹脂組成物。
- 前記S成分、前記M成分、及び前記L成分の合計に対する前記L成分の比(L成分/(S成分+M成分+L成分))が、4%以上である、請求項10又は11に記載の樹脂組成物。
- 前記黒鉛(B)が、板状黒鉛である、請求項10~12のいずれか1項に記載の樹脂組成物。
- 前記熱可塑性樹脂(A)が、オレフィン系樹脂を含む、請求項10~13のいずれか1項に記載の樹脂組成物。
- 金型内に溶融状態の前記樹脂組成物を得られる樹脂成形体の厚み方向に直交する方向から充填させて成形し、縦100mm×横100mm×厚み2mmの樹脂成形体を得たときに、
3GHz、25GHz、50GHz、及び75GHzのうちいずれかの周波数における前記樹脂成形体の電磁波シールド効果が、20dB以上である、請求項1~14のいずれか1項に記載の樹脂組成物。 - 金型内に溶融状態の前記樹脂組成物を得られる樹脂成形体の厚み方向に直交する方向から充填させて成形し、縦100mm×横100mm×厚み2mmの樹脂成形体を得たときに、
前記樹脂成形体の面内方向の熱伝導率が、1W/(m・K)以上である、請求項1~15のいずれか1項に記載の樹脂組成物。 - 請求項1~16のいずれか1項に記載の樹脂組成物の成形体である、樹脂成形体。
- 繊維を含む、請求項17に記載の樹脂成形体。
- 体積固有抵抗率が1.0×105Ω・cm以下である、請求項17又は18に記載の樹脂成形体。
- 請求項1~16のいずれか1項に記載の樹脂組成物と、熱可塑性樹脂及び繊維を含む複合体(E)とを混合して混合物を得る工程と、
前記混合物を成形することにより、樹脂成形体を得る工程と、
を備える、樹脂成形体の製造方法。
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