WO2017145957A1 - 熱伝導シートおよびその製造方法、ならびに放熱装置 - Google Patents
熱伝導シートおよびその製造方法、ならびに放熱装置 Download PDFInfo
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- WO2017145957A1 WO2017145957A1 PCT/JP2017/006014 JP2017006014W WO2017145957A1 WO 2017145957 A1 WO2017145957 A1 WO 2017145957A1 JP 2017006014 W JP2017006014 W JP 2017006014W WO 2017145957 A1 WO2017145957 A1 WO 2017145957A1
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- conductive sheet
- heat conductive
- blade
- heat
- resin
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- C08L27/02—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C08L27/12—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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/20—Homopolymers or copolymers of hexafluoropropene
Definitions
- the present invention relates to a heat conductive sheet, a manufacturing method thereof, and a heat dissipation device.
- a method of promoting heat dissipation by attaching a heat sink such as a metal heat sink, heat sink, heat sink or the like to a heat generator such as an electronic component is adopted.
- a heat dissipation body in order to efficiently transfer heat from the heat generation element to the heat dissipation element, a sheet-like member (heat conduction sheet) with high thermal conductivity is passed through this heat conduction sheet.
- the heating element and the radiator are brought into close contact with each other.
- the heat conductive sheet a sheet formed using a composite material sheet having excellent heat conductivity is used.
- a heat conductive sheet used by being sandwiched between such a heat generating body and a heat radiating body has been required to have high flexibility in addition to high heat conductivity.
- the thermal resistance of the material itself ie the bulk thermal resistance
- the interfacial thermal resistance of the heat conductive sheet is the adhesion between the heat generating body and the heat radiating body (interfacial adhesion), the difference in bulk thermal resistance between the heat generating body and the heat conductive sheet, It is known to increase or decrease depending on the difference in thermal resistance.
- the interfacial adhesion can be affected by the pressure applied to the heat conductive sheet, the hardness (flexibility) of the heat conductive sheet, and the like. Therefore, in order to reduce the interfacial thermal resistance of the heat conductive sheet, it has been generally considered to increase the interfacial adhesion by giving a tack to the surface of the heat conductive sheet or reducing the hardness of the heat conductive sheet. .
- a primary sheet is formed from a composition including a thermoplastic rubber, a thermosetting rubber, a thermosetting rubber curing agent, and anisotropic graphite powder, and these are laminated to form a vertical direction.
- a heat conductive sheet having a low thermal resistance of 0.04 ° C./W under 0.5 MPa pressure is obtained in which graphite is oriented in the vertical direction.
- heat treatment is performed to crosslink the thermosetting rubber with a thermosetting rubber curing agent, so that the thermoplastic rubber and the crosslinked thermosetting rubber are obtained. Coexistence improves strength and flexibility.
- Patent Document 2 discloses a heat conductive sheet containing a resin and fibrous carbon fibers.
- the heat conductive sheet is 0.35 ° C. under a pressure of 0.1 MPa by not orienting 45 to 95% of the fibrous carbon fibers contained in the heat conductive sheet in the thickness direction of the heat conductive sheet. A thermal resistance of / W is achieved.
- Patent Document 3 discloses a heat conductive silicone grease composition containing silicone oil and copper powder having a low oxygen content.
- the coarse particle mass is decreased by using copper powder having a small average particle diameter, and the film thickness when applied is reduced to 0.036 ° C. under a pressure of 0.15 MPa. A sufficiently low thermal resistance of / W is achieved.
- the thermal conductive sheet of Patent Document 1 has excellent thermal conductivity only under a high pressure of 0.5 MPa, and the thermal conductivity is greatly reduced under a low pressure of 0.1 MPa. Further, the adhesiveness is imparted more than necessary to reduce the interfacial thermal resistance, and the workability and peelability at the time of attachment and replacement are inferior, and the sheet component remains in the housing of the heat dissipation device at the time of replacement. Further, the thermal conductive sheet of Patent Document 2 has the lowest thermal resistance under a relatively low pressure of 0.1 MPa, but the thermal resistance value itself of 0.35 ° C./W under the pressure is high and excellent. It cannot be said that it exhibits thermal conductivity and heat dissipation characteristics.
- thermal conductive silicone grease composition of Patent Document 3 can exhibit excellent thermal conductivity under a relatively low pressure region such as 0.15 MPa, but because of grease rather than a sheet, the peelability is very poor, Reworkability is inferior, such as difficult to replace. That is, there has been no heat conductive sheet excellent in handleability and heat conductivity under a relatively low pressure.
- an object of this invention is to provide the heat conductive sheet which is excellent in handleability and excellent in heat conductivity under a comparatively low pressure.
- excellent handleability means that the balance between hardness and adhesiveness is excellent, and the workability at the time of attachment and replacement is excellent.
- relatively low pressure refers to 0.1 MPa or less. It is another object of the present invention to provide a heat dissipation device having excellent heat dissipation characteristics under a relatively low pressure.
- a heat conductive sheet formed using a composition containing a resin and a particulate carbon material and having a predetermined thermal resistance value has excellent thermal conductivity under a relatively low pressure, and is easy to handle.
- the present invention was completed.
- the heat conductive sheet of this invention contains resin and a particulate carbon material,
- the value of the thermal resistance under 0.05 Mpa pressurization Is 0.20 ° C./W or less. Since the heat conductive sheet having such a configuration is excellent in balance between hardness and adhesiveness, it is excellent in handleability and can have excellent heat conductivity and heat dissipation characteristics under a relatively low pressure.
- the rate of change of the thermal resistance value when the applied pressure is changed from 0.50 MPa to 0.05 MPa is + 150.0% or less. If the rate of change of the thermal resistance value when the applied pressure is changed from 0.50 MPa to 0.05 MPa is + 150.0% or less, it is possible to improve the balance between hardness and adhesiveness and improve the handleability. it can.
- the tack measured by the probe tack test is preferably 1.40 N or less.
- the tack measured in the probe tack test is 1.40 N or less, it shows a good adhesion at the time of use, and has a good peelability at the time of mounting and replacement.
- the heat conductive sheet can be removed without destroying the heat conductive sheet, that is, without leaving a part or all of the heat conductive sheet in the attachment.
- the particulate carbon material is preferably 20 parts by mass or more with respect to 100 parts by mass of the resin.
- the handling property can be further improved and the thermal resistance can be reduced.
- the resin is a thermoplastic resin
- the thermoplastic resin is a room temperature liquid thermoplastic resin.
- the resin is a thermoplastic resin
- the balance between the hardness and the adhesiveness of the heat conductive sheet can be further improved, and the handleability can be further improved.
- the thermoplastic resin is a room temperature liquid thermoplastic resin, it is possible to increase the interfacial adhesion and decrease the interfacial thermal resistance even under a relatively low pressure, and to reduce the thermal conductivity of the thermal conductive sheet (ie, heat dissipation). Characteristics) can be improved.
- the heat dissipating device of the present invention is characterized in that the heat conductive sheet of the present invention is interposed between the heat generating body and the heat dissipating body. Excellent heat dissipation characteristics at relatively low pressures by interposing the heat conductive sheet of the present invention between the heating element and the heat dissipation element with excellent handling properties and excellent thermal conductivity under relatively low pressure. can do.
- the manufacturing method of the heat conductive sheet of the present invention is as follows: Pressurizing a composition containing a resin and a particulate carbon material to form a sheet, and obtaining a pre-heat conductive sheet; Laminating a plurality of the pre-heat conductive sheets in the thickness direction, or folding or winding the pre-heat conductive sheets to obtain a laminate; Slicing the laminated body at an angle of 45 ° or less with respect to the laminating direction to obtain a heat conductive sheet.
- the particulate carbon materials are arranged in the thickness direction, so that not only the heat conductivity in the thickness direction but also the conductivity can be improved.
- the heat conductive sheet of the present invention can be used, for example, by being sandwiched between a heat generator and a heat radiator when the heat radiator is attached to the heat generator. That is, the heat conductive sheet of this invention can comprise a heat radiating device with a heat generating body and heat radiating bodies, such as a heat sink, a heat sink, and a heat radiating fin. And the heat conductive sheet of this invention can be manufactured, for example using the manufacturing method of the heat conductive sheet of this invention.
- the heat conductive sheet of the present invention includes a resin and a particulate carbon material, and has a heat resistance value under a pressure of 0.05 MPa of 0.20 ° C./W or less.
- a pressure of 0.05 MPa of 0.20 ° C./W or less When the heat conductive sheet does not contain a particulate carbon material, sufficient heat conductivity cannot be obtained. Moreover, when the heat conductive sheet does not contain a resin, sufficient flexibility cannot be obtained.
- the resin is not particularly limited, and a known resin that can be used for forming the heat conductive sheet can be used. Among them, a thermoplastic resin is preferably used. If a thermoplastic resin is used, the flexibility of the heat conductive sheet can be further improved in a high temperature environment during use (heat dissipation), and the heating element and the heat dissipation element can be satisfactorily adhered to each other via the heat conductive sheet. Because. Further, as the resin, a thermosetting resin can be used in combination as long as the characteristics and effects of the heat conductive sheet of the present invention are not lost. In the present invention, rubber and elastomer are included in “resin”.
- thermoplastic resins that can be used to form the thermal conductive sheet include room temperature solid thermoplastic resins, room temperature liquid thermoplastic resins, and the like.
- room temperature refers to 23 ° C.
- the interfacial adhesion can be increased and the interfacial thermal resistance can be lowered even under relatively low pressure, and the thermal conductivity (ie, heat dissipation characteristics) of the thermal conductive sheet can be improved. Can do.
- normal temperature liquid thermoplastic resin examples include acrylic resin, epoxy resin, silicone resin, and fluororesin. These may be used individually by 1 type and may use 2 or more types together.
- a room temperature solid thermoplastic resin can be used in combination with a room temperature liquid thermoplastic resin.
- the room temperature solid thermoplastic resin include poly (2-ethylhexyl acrylate), a copolymer of acrylic acid and 2-ethylhexyl acrylate, polymethacrylic acid or an ester thereof, and acrylic such as polyacrylic acid or an ester thereof.
- thermoplastic fluororesin The thermoplastic resin contained in the heat conductive sheet of the present invention preferably contains a thermoplastic fluororesin, and more preferably consists of a thermoplastic fluororesin.
- a thermoplastic fluororesin As the thermoplastic resin, heat resistance, oil resistance, and chemical resistance can be improved.
- the thermoplastic resin contained in the heat conductive sheet of the present invention is more preferably a normal temperature liquid thermoplastic fluororesin.
- thermoplastic fluororesin at room temperature as the thermoplastic resin, it increases interfacial adhesion and reduces interfacial thermal resistance even under relatively low pressure.
- the thermal conductivity (that is, the heat dissipation characteristics) of the thermal conductive sheet can be improved.
- the room temperature liquid thermoplastic fluororesin is not particularly limited as long as it is a liquid fluororesin at room temperature (23 ° C.).
- vinylidene fluoride / hexafluoropropylene copolymer vinylidene fluoride-hexafluoropentene-tetrafluoroethylene terpolymer, perfluoropropene oxide polymer, tetrafluoroethylene-propylene-vinylidene fluoride copolymer, etc. Is mentioned.
- Viton (registered trademark) LM manufactured by DuPont
- Daiel registered trademark
- G101 manufactured by Daikin Industries, Ltd.
- Dinion FC2210 manufactured by 3M Corporation
- SIFEL series Commercial products such as those manufactured by Shin-Etsu Chemical Co., Ltd. can also be used.
- the viscosity of the normal temperature liquid thermoplastic fluororesin is not particularly limited, but the viscosity at 105 ° C. is 500 to 30,000 cps from the viewpoint of good kneadability, fluidity, cross-linking reactivity and excellent moldability. It is preferably 550 to 25,000 cps.
- a room temperature solid thermoplastic fluororesin can be used in combination with a room temperature solid thermoplastic fluororesin.
- the room temperature solid thermoplastic fluororesin include elastomers obtained by polymerizing a fluorine-containing monomer, such as vinylidene fluoride, tetrafluoroethylene-propylene, tetrafluoroethylene-purple chlorovinyl ether, and the like.
- polytetrafluoroethylene tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-ethylene copolymer, polyvinylidene fluoride, polychloro Trifluoroethylene, ethylene-chlorofluoroethylene copolymer, tetrafluoroethylene-perfluorodioxole copolymer, polyvinyl fluoride, tetrafluoroethylene-propylene copolymer, vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene Copolymer, polytetrafluoroethylene modified acrylic, polytetrafluoroethylene ester modified, polytetrafluoroethylene epoxy modified and polytet Silane-modified products of fluoro ethylene.
- polytetrafluoroethylene polytetrafluoroethylene modified acrylic, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer Is preferred.
- thermosetting resin examples include, for example, natural rubber; butadiene rubber; isoprene rubber; nitrile rubber; Chloroprene rubber; Ethylene propylene rubber; Chlorinated polyethylene; Chlorosulfonated polyethylene; Butyl rubber; Halogenated butyl rubber; Polyisobutylene rubber; Epoxy resin; Polyimide resin; Bismaleimide resin; Benzocyclobutene resin; Diallyl phthalate resin; polyimide silicone resin; polyurethane; thermosetting polyphenylene ether; thermosetting modified polyphenylene ether; These may be used individually by 1 type and may use 2 or more types together.
- the particulate carbon material is not particularly limited, and examples thereof include artificial graphite, flaky graphite, exfoliated graphite, natural graphite, acid-treated graphite, expandable graphite, expanded graphite, and the like; carbon black; Can be used. These may be used individually by 1 type and may use 2 or more types together. Among them, it is preferable to use expanded graphite as the particulate carbon material. This is because if the expanded graphite is used, the thermal conductivity of the thermal conductive sheet can be improved.
- the expanded graphite that can be suitably used as the particulate carbon material is, for example, finely expanded after heat-treating expandable graphite obtained by chemically treating graphite such as scaly graphite with sulfuric acid or the like. Can be obtained.
- expanded graphite include EC1500, EC1000, EC500, EC300, EC100, and EC50 (all trade names) manufactured by Ito Graphite Industries Co., Ltd.
- the average particle diameter of the particulate carbon material contained in the heat conductive sheet of the present invention is preferably 0.1 ⁇ m or more, more preferably 1 ⁇ m or more, and further preferably 25 ⁇ m or more. Preferably, it is 300 ⁇ m or less, more preferably 250 ⁇ m or less, and further preferably 200 ⁇ m or less. If the average particle diameter of the particulate carbon material is within the above range, the balance between the hardness and the adhesiveness of the heat conductive sheet can be further improved to improve the handleability, and the thermal resistance of the heat conductive sheet can be further increased. This is because the thermal conductivity can be improved by lowering.
- the aspect ratio (major axis / minor axis) of the particulate carbon material contained in the heat conductive sheet of the present invention is preferably 1 or more and 10 or less, and more preferably 1 or more and 5 or less.
- average particle diameter refers to a cross section in the thickness direction of the heat conductive sheet observed with a scanning electron microscope (SEM), and the maximum diameter (major diameter) of any 50 particulate carbon materials is measured. The number average value of the measured major axis can be calculated.
- the “aspect ratio” is the maximum diameter (major diameter) of any 50 particulate carbon materials observed by a SEM (scanning electron microscope) in the thickness direction of the heat conductive sheet. It can be determined by measuring the particle diameter (minor axis) in the direction orthogonal to the maximum diameter and calculating the average value of the ratio of the major axis to the minor axis (major axis / minor axis).
- the content rate of the particulate carbon material in the heat conductive sheet of the present invention is preferably 20 parts by mass or more, more preferably 30 parts by mass or more with respect to 100 parts by mass of the resin, and 50 parts by mass. More preferably, it is 150 parts by mass or less, more preferably 90 parts by mass or less, and still more preferably 80 parts by mass or less. If the content ratio of the particulate carbon material in the heat conductive sheet is 20 parts by mass or more and 150 parts by mass or less with respect to 100 parts by mass of the resin, the balance between the hardness and the adhesiveness of the heat conductive sheet is further improved. The handling property can be further improved.
- the content rate of a particulate carbon material is 20 mass parts or more with respect to 100 mass parts of resin, the heat conductivity of a heat conductive sheet can be improved. Moreover, if the content rate of a particulate carbon material is 150 mass parts or less with respect to 100 mass parts of resin, it will improve the adhesiveness of a heat conductive sheet, and fully prevent the particulate carbon material from falling off. Can do.
- the heat conductive sheet of the present invention may optionally contain a fibrous carbon material.
- the fibrous carbon material optionally contained is not particularly limited, and for example, carbon nanotubes, vapor-grown carbon fibers, carbon fibers obtained by carbonizing organic fibers, and cut products thereof are used. Can do. These may be used individually by 1 type and may use 2 or more types together. And if fibrous carbon material is contained in the heat conductive sheet of this invention, while being able to improve thermal conductivity further, powdered-off of particulate carbon material can also be prevented.
- the fibrous carbon material it is preferable to use a fibrous carbon nanostructure such as a carbon nanotube, and it is more preferable to use a fibrous carbon nanostructure including a carbon nanotube. This is because the use of fibrous carbon nanostructures such as carbon nanotubes can further improve the thermal conductivity and strength of the thermal conductive sheet of the present invention.
- the fibrous carbon nanostructure containing carbon nanotubes that can be suitably used as the fibrous carbon material may be composed only of carbon nanotubes (hereinafter sometimes referred to as “CNT”).
- CNT carbon nanotubes
- a mixture of CNT and a fibrous carbon nanostructure other than CNT may be used.
- the CNT in the fibrous carbon nanostructure is not particularly limited, and single-walled carbon nanotubes and / or multi-walled carbon nanotubes can be used. Nanotubes are preferable, and single-walled carbon nanotubes are more preferable. This is because if single-walled carbon nanotubes are used, the thermal conductivity and strength of the thermal conductive sheet of the present invention can be further improved as compared with the case where multi-walled carbon nanotubes are used.
- the fibrous carbon nanostructure containing CNT has a ratio (3 ⁇ / Av) of a value (3 ⁇ ) obtained by multiplying the standard deviation ( ⁇ ) of the diameter by 3 with respect to the average diameter (Av) is more than 0.20. It is preferable to use a carbon nanostructure of less than 0.60, more preferably a carbon nanostructure with 3 ⁇ / Av exceeding 0.25, and a carbon nanostructure with 3 ⁇ / Av exceeding 0.50. More preferably. If a fibrous carbon nanostructure containing CNTs with 3 ⁇ / Av of more than 0.20 and less than 0.60 is used, the heat conduction of the heat conductive sheet of the present invention is achieved even if the amount of carbon nanostructure is small. The strength and strength can be sufficiently increased.
- the heat conduction of the heat conductive sheet of the present invention is suppressed by suppressing the increase in the hardness (that is, the flexibility is lowered) of the heat conductive sheet of the present invention by blending the fibrous carbon nanostructure containing CNT. Sex and flexibility can be juxtaposed at a sufficiently high level.
- Average diameter (Av) of fibrous carbon nanostructure” and “standard deviation of diameter of fibrous carbon nanostructure ( ⁇ : sample standard deviation)” are measured using a transmission electron microscope, respectively. It can be determined by measuring the diameter (outer diameter) of 100 randomly selected fibrous carbon nanostructures.
- the average diameter (Av) and standard deviation ( ⁇ ) of the fibrous carbon nanostructure containing CNT are adjusted by changing the manufacturing method and manufacturing conditions of the fibrous carbon nanostructure containing CNT. Alternatively, it may be adjusted by combining a plurality of types of fibrous carbon nanostructures containing CNTs obtained by different production methods.
- the diameter measured as described above is plotted on the horizontal axis
- the frequency is plotted on the vertical axis
- a normal distribution is obtained when approximated by Gaussian. Things are usually used.
- the fibrous carbon nanostructure containing CNTs preferably has a peak of Radial Breathing Mode (RBM) when evaluated using Raman spectroscopy. Note that there is no RBM in the Raman spectrum of a fibrous carbon nanostructure composed of only three or more multi-walled carbon nanotubes.
- RBM Radial Breathing Mode
- the fibrous carbon nanostructure containing CNTs preferably has a G-band peak intensity ratio (G / D ratio) of 1 to 20 in the Raman spectrum.
- G / D ratio is 1 or more and 20 or less
- the thermal conductivity and strength of the thermal conductive sheet of the present invention can be sufficiently increased even if the blending amount of the fibrous carbon nanostructure is small. Therefore, the thermal conductivity and flexibility of the heat conductive sheet of the present invention are sufficiently suppressed by suppressing the increase in the hardness of the heat conductive sheet (that is, the flexibility is lowered) by blending the fibrous carbon nanostructure. Can be juxtaposed at a high level.
- the average diameter (Av) of the fibrous carbon nanostructure containing CNTs is preferably 0.5 nm or more, more preferably 1 nm or more, preferably 15 nm or less, and preferably 10 nm or less. More preferably it is.
- the average diameter (Av) of the fibrous carbon nanostructure is 0.5 nm or more, aggregation of the fibrous carbon nanostructure can be suppressed and the dispersibility of the carbon nanostructure can be improved.
- the average diameter (Av) of fibrous carbon nanostructure is 15 nm or less, the heat conductivity and intensity
- the fibrous carbon nanostructure containing CNTs preferably has an average length of the structure at the time of synthesis of 100 ⁇ m or more and 5000 ⁇ m or less. Note that, as the length of the structure at the time of synthesis increases, damage such as breakage or cutting occurs more easily at the time of dispersion. Therefore, the average length of the structure at the time of synthesis is preferably 5000 ⁇ m or less.
- the BET specific surface area of the fibrous carbon nanostructure containing CNTs is preferably 600 m 2 / g or more, more preferably 800 m 2 / g or more, and 2500 m 2 / g or less. Preferably, it is 1200 m 2 / g or less. Furthermore, when the CNT in the fibrous carbon nanostructure is mainly opened, the BET specific surface area is preferably 1300 m 2 / g or more. If the BET specific surface area of the fibrous carbon nanostructure containing CNT is 600 m 2 / g or more, the thermal conductivity and strength of the thermal conductive sheet of the present invention can be sufficiently increased.
- the BET specific surface area of the fibrous carbon nanostructure containing CNT is 2500 m 2 / g or less, the aggregation of the fibrous carbon nanostructure is suppressed and the dispersion of CNT in the heat conductive sheet of the present invention is suppressed. Can increase the sex.
- the “BET specific surface area” refers to a nitrogen adsorption specific surface area measured using the BET method.
- the fibrous carbon nanostructure containing CNTs is an aggregate oriented in a direction substantially perpendicular to the base material on the base material having a catalyst layer for carbon nanotube growth on the surface according to the super growth method described later.
- the mass density of the fibrous carbon nanostructure as the aggregate is preferably 0.002 g / cm 3 or more and 0.2 g / cm 3 or less. If the mass density is 0.2 g / cm 3 or less, since the bonds between the fibrous carbon nanostructures are weakened, the fibrous carbon nanostructures can be uniformly dispersed in the heat conductive sheet.
- the mass density is 0.002 g / cm 3 or more, the integrity of the fibrous carbon nanostructure can be improved, and the handling can be easily performed because the disintegration can be suppressed.
- the fibrous carbon nanostructure containing CNTs having the above-described properties can be obtained by, for example, supplying a raw material compound and a carrier gas onto a substrate having a catalyst layer for producing carbon nanotubes on the surface,
- CVD method phase growth method
- oxidizing agent catalyst activation material
- the fibrous carbon nanostructure containing CNT produced by the super-growth method may be composed only of SGCNT, and in addition to SGCNT, other carbon nanostructures such as non-cylindrical carbon nanostructures may be used. Carbon nanostructures may be included.
- the average fiber diameter of the fibrous carbon material that can be contained in the heat conductive sheet is preferably 1 nm or more, more preferably 3 nm or more, preferably 2 ⁇ m or less, and preferably 1 ⁇ m or less. More preferred. This is because if the average fiber diameter of the fibrous carbon material is within the above range, the thermal conductivity, flexibility and strength of the thermal conductive sheet can be juxtaposed at a sufficiently high level.
- the aspect ratio of the fibrous carbon material preferably exceeds 10.
- the “average fiber diameter” refers to any 50 fibrous carbon materials obtained by observing a cross section in the thickness direction of the heat conductive sheet with an SEM (scanning electron microscope) or TEM (transmission electron microscope). Can be determined by measuring the fiber diameter and calculating the number average value of the measured fiber diameters. In particular, when the fiber diameter is small, it is preferable to observe the same cross section with a TEM (transmission electron microscope).
- the content rate of the fibrous carbon material in the heat conductive sheet of this invention is preferably 0.05 mass% or more, more preferably 0.2 mass% or more, and 5 mass% or less. It is preferably 3% by mass or less. If the content ratio of the fibrous carbon material in the thermal conductive sheet is 0.05% by mass or more, the thermal conductivity and strength of the thermal conductive sheet can be sufficiently improved, and the particulate carbon material can be powdered off. This is because it can be sufficiently prevented.
- the content ratio of the fibrous carbon material in the heat conductive sheet is 5% by mass or less, the hardness of the heat conductive sheet is prevented from being increased (that is, the flexibility is lowered) by blending the fibrous carbon material. Then, the heat conductivity and flexibility of the heat conductive sheet of the present invention can be juxtaposed at a sufficiently high level.
- the heat conductive sheet of the present invention can be blended with known additives that can be used for forming the heat conductive sheet, if necessary.
- Additives that can be blended in the heat conductive sheet are not particularly limited, for example, plasticizers such as fatty acid esters; flame retardants such as red phosphorus flame retardants and phosphate ester flame retardants; urethane acrylates and the like Toughness improvers; hygroscopic agents such as calcium oxide and magnesium oxide; adhesive strength improvers such as silane coupling agents, titanium coupling agents, and acid anhydrides; wettability such as nonionic surfactants and fluorosurfactants Improvers; ion trapping agents such as inorganic ion exchangers; and the like.
- thermo conductive sheet the heat conductive sheet of this invention is not specifically limited, It is preferable to have the following properties.
- the value of the thermal resistance under a pressure of 0.05 MPa is 0.20 ° C./W or less, more preferably 0.19 ° C./W or less, and 0.17 ° C./W or less. More preferably.
- the value of the thermal resistance under 0.05 MPa pressurization is 0.20 ° C./W or less, excellent thermal conductivity can be obtained in a use environment where a relatively low pressure is applied.
- the value of the thermal resistance can be measured by using a known measurement method that is usually used for measuring the thermal resistance of the heat conductive sheet, and a resin material thermal resistance tester (for example, Hitachi Technology & Service Co., Ltd.). Product name, “C47108”) and the like.
- the rate of change of the thermal resistance value when the applied pressure is changed from 0.50 MPa to 0.05 MPa is preferably + 150.0% or less, and + 120.0% or less. More preferably, it is more preferably + 115.0% or less.
- the rate of change of the thermal resistance value when the applied pressure is changed from 0.50 MPa to 0.05 MPa is + 150.0% or less, the range of increase in the thermal resistance value due to the decrease in the applied pressure is small, and more than a certain value Of hardness. Therefore, the balance between hardness and adhesiveness can be improved, and handling properties can be improved.
- the rate of change of the thermal resistance value when the applied pressure is reduced from 0.5 MPa to 0.05 MPa can be calculated by the following formula: 100 ⁇ (thermal resistance value under 0.05 MPa pressure ⁇ 0 Thermal resistance value under 0.5 MPa pressure) / thermal resistance value (%) under 0.5 MPa pressure.
- the heat conductive sheet of the present invention has a tack measured by a probe tack test of preferably 1.40 N or less, more preferably 1.30 N or less, and even more preferably 1.20 N or less.
- “Tack” means a property of adhering to an adherend in a short time with a light force as defined in JIS Z0109: 2015, and is also referred to as “adhesiveness” in the present specification.
- the tack of the heat conductive sheet of the present invention is measured by a probe tack test. Specifically, when a flat probe having a diameter of 10 mm is pressed against a thermal conductive sheet to be measured for 10 seconds under a temperature condition of 25 ° C.
- the probe is pulled away from the thermal conductive sheet. Measured as the force required.
- the tack measured in the probe tack test is 1.40 N or less, it shows a good adhesion at the time of use, and has a good peelability at the time of mounting and replacement.
- the heat conductive sheet can be removed without destroying the heat conductive sheet, that is, without leaving the heat conductive sheet component in the attachment. In other words, the smaller the tack value measured in the probe tack test, the better the handleability.
- the tack of the heat conductive sheet of the present invention can be measured with a probe tack tester (for example, trade name “TAC1000” manufactured by Resuka Co., Ltd.).
- the heat conductive sheet of the present invention has an Asker C hardness at 25 ° C. of 60 or more, preferably 65 or more, and more preferably 70 or more. If Asker C hardness at 25 ° C. is 60 or more, it can have an appropriate hardness at room temperature, and workability at the time of attachment and replacement can be improved.
- the heat conductive sheet of the present invention preferably has an Asker C hardness at 25 ° C. of 80 or less, more preferably 70 or less. If the Asker C hardness at 25 ° C. is 80 or less, sufficient tackiness can be obtained in a room temperature environment, and workability at the time of attachment and replacement can be further improved.
- the “Asker C hardness” can be measured at a predetermined temperature using a hardness meter in accordance with the Asker C method of the Japan Rubber Association Standard (SRIS).
- SRIS Japan Rubber Association Standard
- the heat conductive sheet of the present invention preferably has an Asker C hardness of 55 or more at 70 ° C., more preferably 60 or more. If the Asker C hardness at 70 ° C. is 55 or more, sufficient hardness can be maintained even in a high temperature environment during use (during heat dissipation), and the releasability at the time of replacement is sufficient, Exchange can be made without leaving the heat conductive sheet component in the housing. Further, the heat conductive sheet of the present invention has an Asker C hardness at 70 ° C. of preferably 70 or less, and more preferably 65 or less. When the Asker C hardness at 70 ° C. is 70 or less, the interfacial adhesion can be further improved in a high temperature environment during use (during heat dissipation), and the thermal conductivity can be further improved.
- the thermal conductivity sheet has a thermal conductivity in the thickness direction of preferably 20 W / m ⁇ K or more at 25 ° C., more preferably 30 W / m ⁇ K or more, and 40 W / m ⁇ K or more. More preferably. If the thermal conductivity is 20 W / m ⁇ K or more, for example, when a heat conductive sheet is sandwiched between a heating element and a radiator, heat can be efficiently transferred from the heating element to the radiator. it can.
- the thickness of the heat conductive sheet is preferably 0.05 mm (50 ⁇ m) to 10 mm. As long as the heat conductive sheet of the present invention does not impair the handleability, the bulk thermal resistance of the heat conductive sheet can be reduced as the thickness is reduced, and the heat conductivity and heat dissipation characteristics when used in a heat dissipation device are reduced. Can be improved.
- the heat conducting sheet of the invention preferably has density of 1.8 g / cm 3 or less, more preferably 1.6 g / cm 3 or less. This is because such a heat conductive sheet has high versatility and can contribute to weight reduction of the electronic component when mounted on a product such as an electronic component.
- a pre-heat conductive sheet is obtained by pressurizing a composition containing a resin and a particulate carbon material, optionally further containing a fibrous carbon material and / or an additive, into a sheet shape. .
- the composition can be prepared by mixing the resin and the particulate carbon material and any fibrous carbon material and / or additive. And as resin, particulate carbon material, fibrous carbon material, and additive, what was mentioned above as resin, particulate carbon material, fibrous carbon material, and additive which can be contained in the heat conductive sheet of this invention is used. Can do.
- the heat conductive sheet resin is a cross-linked resin
- a pre-heat conductive sheet may be formed using a composition containing the cross-linkable resin, or a cross-linkable resin and a curing agent may be used.
- a pre-heat conductive sheet may be formed using the composition contained, and a cross-linkable resin may be contained in the heat conductive sheet by crosslinking a cross-linkable resin after the pre-heat conductive sheet forming step.
- mixing can be performed using known mixing apparatuses, such as a kneader, a roll, a Henschel mixer, and a Hobart mixer, without being specifically limited.
- Mixing may be performed in the presence of a solvent such as ethyl acetate.
- the resin may be dissolved or dispersed in a solvent in advance to form a resin solution, which may be mixed with other carbon materials and optional additives.
- the mixing time can be, for example, 5 minutes or more and 6 hours or less.
- the mixing temperature can be, for example, 5 ° C. or more and 150 ° C. or less.
- fibrous carbon materials tend to aggregate and have low dispersibility. Therefore, when mixed with other components such as resin and expanded graphite as they are, they disperse well in the composition. It is hard to do.
- the fibrous carbon material can suppress the occurrence of aggregation by mixing with other components such as resin and expanded graphite in the state of dispersion dispersed in a solvent (dispersion medium), In the case of mixing in a state, a large amount of solvent is used when the solid content is solidified after mixing to obtain a composition, so that the amount of the solvent used for preparing the composition may increase.
- the fibrous carbon material when a fibrous carbon material is blended in the composition used to form the pre-heat conductive sheet, the fibrous carbon material is a solvent from a dispersion obtained by dispersing the fibrous carbon material in a solvent (dispersion medium). It is preferable to mix with other components in the state of an aggregate (easily dispersible aggregate) of fibrous carbon materials obtained by removing.
- the aggregate of the fibrous carbon material obtained by removing the solvent from the dispersion of the fibrous carbon material is composed of the fibrous carbon material once dispersed in the solvent, and the fibrous carbon material before being dispersed in the solvent. Since the dispersibility is superior to that of the above-mentioned aggregate, it becomes an easily dispersible aggregate with high dispersibility. Therefore, if the easily dispersible aggregate is mixed with other components such as resin and expanded graphite, the fibrous carbon material is efficiently dispersed in the composition efficiently without using a large amount of solvent. be able to.
- the dispersion of the fibrous carbon material for example, a coarse dispersion obtained by adding the fibrous carbon material to the solvent is subjected to a dispersion treatment that provides a cavitation effect or a dispersion treatment that obtains a crushing effect. Can be obtained.
- the dispersion process which can obtain a cavitation effect is a dispersion method using a shock wave generated when a vacuum bubble generated in water bursts when high energy is applied to a liquid.
- Specific examples of the dispersion treatment that can provide a cavitation effect include dispersion treatment using an ultrasonic homogenizer, dispersion treatment using a jet mill, and dispersion treatment using a high shear stirrer.
- the dispersion treatment that provides the crushing effect is to apply shear force to the coarse dispersion liquid to crush and disperse the aggregates of the fibrous carbon material, and further to apply a back pressure to the coarse dispersion liquid.
- This is a dispersion method in which the fibrous carbon material is uniformly dispersed in a solvent while suppressing generation.
- distribution process from which a crushing effect is acquired can be performed using a commercially available dispersion
- the solvent can be removed from the dispersion using a known solvent removal method such as drying or filtration. From the viewpoint of removing the solvent quickly and efficiently, filtration such as vacuum filtration is used. It is preferable to carry out.
- composition prepared as described above can be defoamed and crushed arbitrarily, and then pressed to form a sheet.
- a solvent is used at the time of mixing, it is preferable to form the sheet after removing the solvent. For example, if defoaming is performed using vacuum defoaming, the solvent is simultaneously removed at the time of defoaming. be able to.
- the composition can be formed into a sheet using a known forming method such as press forming, rolling forming, or extrusion forming without particular limitation as long as it is a forming method in which pressure is applied.
- the composition is preferably formed into a sheet by rolling, and more preferably formed into a sheet by passing between rolls in a state of being sandwiched between protective films.
- a protective film the polyethylene terephthalate film etc. which performed the sandblast process etc. can be used, without being specifically limited.
- the roll temperature can be 5 ° C. or more and 150 ° C.
- the particulate carbon materials are arranged mainly in the in-plane direction, and particularly when the heat conductivity in the in-plane direction of the pre-heat conductive sheet is improved.
- the thickness of a pre heat conductive sheet is not specifically limited, For example, it can be 0.05 mm or more and 2 mm or less. From the viewpoint of further improving the thermal conductivity of the heat conductive sheet, the thickness of the pre-heat conductive sheet is preferably more than 20 times and not more than 5000 times the average particle diameter of the particulate carbon material.
- laminated body forming step a plurality of pre heat conductive sheets obtained in the pre heat conductive sheet forming step are laminated in the thickness direction, or the pre heat conductive sheets are folded or wound to obtain a laminate.
- formation of the laminated body by folding of a pre heat conductive sheet is not specifically limited, It can carry out by folding a pre heat conductive sheet by fixed width using a folding machine.
- the formation of the laminate by winding the pre-heat conductive sheet is not particularly limited, and by rolling the pre-heat conductive sheet around an axis parallel to the short direction or the long direction of the pre-heat conductive sheet It can be carried out.
- the adhesive force between the surfaces of the pre-heat conductive sheets is sufficient by the pressure when laminating the pre-heat conductive sheets and the pressure when folding or winding. Is obtained.
- the laminate forming step may be performed with the surface of the pre-heat conductive sheet slightly dissolved with a solvent.
- the laminated body forming step may be performed in a state where an adhesive is applied to the surface of the pre-heat conductive sheet or a state where an adhesive layer is provided on the surface of the pre-heat conductive sheet.
- dissolving the surface of a pre heat conductive sheet it is not specifically limited, The known solvent which can melt
- coated to the surface of a pre heat conductive sheet A commercially available adhesive agent and adhesive resin can be used.
- the adhesive it is preferable to use a resin having the same composition as the resin component contained in the pre-heat conductive sheet.
- coated to the surface of a pre heat conductive sheet can be 10 micrometers or more and 1000 micrometers or less, for example.
- the adhesive layer provided on the surface of the pre-heat conductive sheet is not particularly limited, and a double-sided tape or the like can be used.
- the obtained laminate can be pressed at 20 ° C. or more and 100 ° C. or less for 1 to 30 minutes while being pressed at a pressure of 0.05 MPa or more and 1.0 MPa or less in the lamination direction. preferable.
- a fibrous carbon material when added to the composition, or when expanded graphite is used as the particulate carbon material, a laminate obtained by laminating, folding or winding a pre-heat conductive sheet, It is inferred that the expanded graphite and the fibrous carbon material are arranged in a direction substantially orthogonal to the stacking direction.
- the laminated body obtained in the laminated body forming step is sliced at an angle of 45 ° or less with respect to the laminating direction to obtain a heat conductive sheet composed of sliced pieces of the laminated body.
- the method for slicing the laminate is not particularly limited, and examples thereof include a multi-blade method, a laser processing method, a water jet method, and a knife processing method.
- the knife processing method is preferable at the point which makes the thickness of a heat conductive sheet uniform.
- the cutting tool for slicing the laminate is not particularly limited, and includes a slice member (for example, a sharp blade) having a smooth board surface having a slit and a blade portion protruding from the slit portion. Canna and slicer) can be used.
- a slice member for example, a sharp blade
- Canna and slicer can be used.
- the single blade provided with the blade portion may be a “double blade” in which both the front and back sides of the blade edge are cutting blades, or may be a “single blade” in which only the front side of the blade is a cutting blade.
- FIGS. 1 to 4 which are cross-sectional views of the blade edge 1, both blades have cutting edges 2 and 3 on both the left and right sides (FIGS. 1 to 3). 2 (FIG. 4).
- the cross-sectional shape of the blade edge 1 is not particularly limited, and may be asymmetric or symmetric with respect to the central axis 4 passing through the leading edge of the blade edge 1.
- a blade whose shape is symmetrical with respect to the central axis is referred to as “symmetric blade” (FIG. 2)
- a blade whose shape is asymmetric with respect to the central axis is referred to as “asymmetric blade” (FIG. 3).
- the angles formed by the cutting edges on both the left and right sides with respect to the central axis are respectively referred to as “center angles”, and the sum of these central angles is also referred to as the angle of the cutting edge (hereinafter referred to as “blade angle”). ).
- the angle formed by the left cutting edge 2 with respect to the central axis 4 is the central angle a
- the right cutting edge with respect to the central axis 4 is The constituting angle is the central angle b.
- the blade angle is preferably 60 degrees or less.
- the angles of the central angles a and b are not particularly limited, but preferably can be selected so that the blade angle is 60 degrees or less.
- the blade angle is 40 degrees which is the sum of a and b.
- the central angles a and b are different from each other by more than 0 degrees, and preferably the sum of the a and b (blade angle) is 60 degrees or less. Can be selected.
- the center angle a on one side is larger than 0 degree and the other center angle b is 0 degree as shown in FIG. 4, a single blade having one cutting edge 2 and one peak 6 become.
- the central axis 4 is set as follows.
- the “blade height” 10 is defined from the tip of the blade tip to the root of the blade
- the “blade thickness” 11 is defined from the front side 8 to the back side 9 of the blade.
- FIG. 5B is a view of the entire blade 7 shown in FIG. 5A as viewed from the front side 8 of the blade. 6 and 7 in which the entire blade is viewed from the side, a perpendicular line 13 is drawn in the direction from the blade height 10 to the blade thickness 11 in the cross section obtained by cutting the blade in a plane perpendicular to the blade height 10, and the length of the perpendicular line 13 is drawn.
- the longest vertical line is defined as a “reference line” 14 (FIGS. 6A and 7A).
- a vertical line 15 is drawn from the reference line 14 toward the tip of the blade, and the vertical line having the longest vertical line 15 and its extension line are defined as a “central axis” 4 (FIGS. 6B and 7B). As described above, the central axis 4 passes through the forefront of the cutting edge.
- the blade may be a single-stage blade in which one cutting blade 2 or 3 has one surface with respect to the central axis 4 of the blade as shown in FIGS. 1 to 7, as shown in FIG.
- One cutting blade 2 or 3 may be a two-stage blade having two surfaces with different inclination angles with respect to the central axis 4 of the blade.
- the sum of the central angles a and b constituting the tip of the blade edge (second stage) is the blade angle 5.
- the blade angle of the two-stage blade is referred to as “blade angle ⁇ ” for convenience.
- c and d are center angles formed by two-dot chain lines obtained by extending the root angle side (first stage) of the blade edge with respect to the center axis 4 of the blade in the cutting edge direction of the blade edge,
- the blade angle 16 which is the sum of c and d is referred to as “blade angle ⁇ ” for convenience.
- the angles of the blade angle ⁇ and the blade angle ⁇ are different from each other and are preferably greater than 0 degree and 60 degrees or less (0 degree ⁇ blade angle ⁇ , blade angle ⁇ ⁇ 60 degrees).
- the blade angle ⁇ is preferably larger than the blade angle ⁇ (blade angle ⁇ > blade angle ⁇ ). This is because curling is thereby suppressed.
- the blade angle ⁇ and the blade angle ⁇ are preferably 0 ° ⁇ blade angle ⁇ ⁇ blade angle ⁇ ⁇ 60 °.
- the number of blades constituting the blade portion is not particularly limited.
- the blade portion may be composed of a single blade composed of one blade, or may be composed of two blades composed of two blades. Good.
- the two-blade is composed of one front blade 17 and one back blade 18, and the front blade 17 and the back blade 18 are blades. Are arranged in contact with each other.
- the blade located on the side closer to the object to be cut is the front blade 17, and the blade farther from the object to be cut is the back blade 18.
- the heights of the cutting edges protruding from the slit portion may be the same or different ( That is, they may be aligned or shifted vertically).
- both the front blade and the back blade may be a single blade (FIG. 9A), both the front blade and the back blade may be a double blade, and either the front blade or the back blade is a single blade. And the other may be double-edged (FIG. 9B).
- the front blade and the back blade is a single blade, as long as the two blades function as a blade (that is, has a cutting function), the side that contacts the blade of the other blade is a cutting blade ( It is not limited to either the front side or the back side. For example, in FIG.
- both the front blade 17 and the back blade 18 are single blades, and contact each other on the peak side, and the leading edge of the cutting edge of the back blade is lower than the leading edge of the cutting edge of the front blade (that is, FIG. 4 is an embodiment of a two-blade arranged offset (down).
- FIG. 9B shows that the front blade 17 is a single blade and the back blade 18 is a double blade, the front blade contacts the back blade on the peak side, and the cutting edge of the back blade is the cutting edge of the front blade.
- FIG. 6 is an embodiment of a two-blade arranged lower (ie down) offset. When one or both of the two blades are both blades, the both blades may be a symmetric blade or an asymmetric blade. Further, each of the two blades may be a one-stage blade or a two-stage blade.
- the material of the blade is not particularly specified and may be any of metal, ceramic and plastic, but cemented carbide is particularly desirable from the viewpoint of withstanding impact. Silicone, fluorine, or the like may be coated on the blade surface for the purpose of improving slipperiness and machinability.
- the angle at which the laminate is sliced is preferably 30 ° or less with respect to the stacking direction, and more preferably 15 ° or less with respect to the stacking direction. Preferably, it is approximately 0 ° with respect to the stacking direction (that is, the direction along the stacking direction).
- the temperature of the laminate during slicing is preferably ⁇ 20 ° C. or more and 40 ° C. or less, and more preferably 10 ° C. or more and 30 ° C. or less.
- the laminated body to be sliced is preferably sliced while applying a pressure in a direction perpendicular to the lamination direction, and a pressure of 0.1 MPa to 0.5 MPa in the direction perpendicular to the lamination direction. It is more preferable to slice while loading.
- the heat conductive sheet obtained in this way it is assumed that the particulate carbon material and the fibrous carbon material are arranged in the thickness direction. Therefore, the heat conductive sheet prepared through the above-described steps has high conductivity as well as heat conductivity in the thickness direction.
- a plurality of heat conductive sheets prepared as described above may be used as a heat conductive sheet by overlapping a plurality of heat conductive sheets in the thickness direction and allowing them to stand for a predetermined time.
- the heat conductive sheet obtained in this way it is assumed that the particulate carbon material and the fibrous carbon material remain arranged in the thickness direction. Therefore, by stacking and integrating a plurality of heat conductive sheets prepared as described above in the thickness direction, a desired thickness can be obtained depending on the purpose of use without impairing the heat conductivity and conductivity in the thickness direction.
- a heat conductive sheet can be obtained.
- the heat conductive sheet manufactured according to the manufacturing method of the present invention is excellent in heat conductivity, strength, and conductivity. Therefore, the composite material sheet and the heat conductive sheet, for example, heat-press the heat-dissipating material, heat-dissipating component, cooling component, temperature adjusting component, electromagnetic wave shielding member, electromagnetic wave absorbing member, and object to be bonded used in various devices and apparatuses. In this case, it is suitable as a rubber sheet for thermocompression bonding interposed between the object to be bonded and the thermocompression bonding apparatus.
- various devices and devices are not particularly limited, and are electronic devices such as servers, server personal computers, and desktop personal computers; portable electronic devices such as notebook computers, electronic dictionaries, PDAs, mobile phones, and portable music players.
- Liquid crystal display including backlight), plasma display, LED, organic EL, inorganic EL, liquid crystal projector, display device such as clock; ink jet printer (ink head), electrophotographic device (developing device, fixing device, heat roller, Image forming apparatuses such as heat belts; semiconductor-related components such as semiconductor elements, semiconductor packages, semiconductor encapsulating cases, semiconductor die bonding, CPUs, memories, power transistors, power transistor cases; rigid wiring boards, flexible wiring boards, ceramic wirings Board, Wiring board such as a folded-up wiring board and multilayer board (the wiring board includes a printed wiring board); manufacturing equipment such as vacuum processing equipment, semiconductor manufacturing equipment, display equipment manufacturing equipment; heat insulating material, vacuum heat insulating material, radiation heat insulating material Thermal insulation equipment for materials, etc .; DVD (optical pickup, laser generator
- the heat dissipating device of the present invention is characterized in that the heat conductive sheet of the present invention is interposed between a heat generating body and a heat dissipating body.
- the operating temperature of the heat dissipating device of the present invention preferably does not exceed 250 ° C., more preferably in the range of ⁇ 20 to 200 ° C. This is because if the use temperature exceeds 250 ° C., the flexibility of the resin component is drastically lowered, and the heat dissipation characteristics may be lowered.
- Examples of the heating element at the use temperature include a semiconductor package, a display, an LED, and an electric lamp.
- a heat sink for example, a heat sink using aluminum, copper fins, plates, etc., an aluminum or copper block connected to a heat pipe, an aluminum or copper that circulates cooling liquid with a pump inside A block, a Peltier element, an aluminum or copper block provided with the same, and the like can be mentioned.
- the heat dissipating device of the present invention can be obtained by interposing the heat conductive sheet of the present invention between the heat generating member and the heat dissipating member and bringing the respective surfaces into contact with each other.
- the contact method There is no particular limitation on the contact method as long as the heat conductive sheet of the present invention is interposed between the heat generating body and the heat dissipating body, and the method can fix them in a sufficiently intimate contact state. Therefore, a contact method in which the pressing force is sustained, such as a method of screwing through a spring and a method of sandwiching with a clip, is preferable.
- the heat dissipating device of the present invention is formed by interposing the heat conductive sheet of the present invention having excellent thermal conductivity under a relatively low pressure between the heat generating member and the heat dissipating member. It can have excellent heat dissipation characteristics in a use environment where a relatively low pressure is applied. Moreover, since the heat conductive sheet of this invention has moderate hardness and adhesiveness, and it is excellent in handling property, the heat radiating device of this invention is excellent in workability
- Thermal resistance value of the heat conductive sheet was performed using a resin material thermal resistance tester (trade name “C47108” manufactured by Hitachi Technology & Service Co., Ltd.). The sample size was cut into 1 cm square, and the thermal resistance value when a constant pressure was applied was measured. The sample temperature was measured to be 50 ° C. It shows that it is excellent in thermal conductivity, and is excellent in the heat dissipation characteristic at the time of interposing between a heat generating body and a heat radiator as a heat resistance value, so that it is small. The pressurizing pressure was evaluated at two points of 0.05 MPa and 0.50 MPa.
- thermal resistance change rate (%) due to pressure drop The rate of change in thermal resistance due to pressure drop can be calculated by the following formula: 100 ⁇ (thermal resistance value under 0.05 MPa pressure ⁇ thermal resistance value under 0.5 MPa pressure) / under 0.5 MPa pressure Thermal resistance value (%).
- ⁇ Tack> The tack of the heat conductive sheet was measured using a probe tack tester (manufactured by Reska Co., Ltd., trade name “TAC1000”). The tip of a flat probe with a diameter of 10 mm was pressed against the resin sheet with a load of 0.5 N (50 gf) for 10 s, and the force required to pull the probe away from the resin sheet was measured. The measurement temperature was 25 ° C. The smaller the measured value of tack, the lower the tackiness, and the better the handleability. When it was too soft to be removed from the probe, it was evaluated as “not measurable”.
- a fibrous carbon nanostructure A containing SGCNT was obtained by the super-growth method according to the description in WO2006 / 011655.
- the obtained fibrous carbon nanostructure A had a G / D ratio of 3.0, a BET specific surface area of 800 m 2 / g, and a mass density of 0.03 g / cm 3 .
- the average diameter (Av) was 3.3 nm
- the sample standard deviation ( ⁇ ) of the diameter (3 ⁇ ) multiplied by 3 was 1.9 nm
- the ratio (3 ⁇ / Av) was 0.58
- the average length was 100 ⁇ m.
- the obtained fibrous carbon nanostructure A was mainly composed of single-walled CNT (also referred to as “SGCNT”).
- Example 1 Preparation of composition> 0.1 part by mass of an easily dispersible aggregate of carbon nanostructure A as a fibrous carbon material and expanded graphite as a particulate carbon material (trade name “EC-100” manufactured by Ito Graphite Industries Co., Ltd.)
- a Hobart mixer Kodaira Manufacturing Co., Ltd.
- 50 parts by mass of an average particle size of 190 ⁇ m and 100 parts by mass of a normal temperature liquid thermoplastic fluororesin made by Daikin Industries, Ltd., trade name “DAIEL G-101”.
- ACM-5LVT type volume: 5 L
- the composition obtained by mixing was put into a Wonder Crush Mill (trade name “D3V-10” manufactured by Osaka Chemical Co., Ltd.) and crushed for 1 minute.
- ⁇ Preparation of pre-heat conductive sheet> Subsequently, 5 g of the crushed composition was sandwiched between 50 ⁇ m-thick PET films (protective film) subjected to sandblast treatment, a roll gap of 550 ⁇ m, a roll temperature of 50 ° C., a roll linear pressure of 50 kg / cm, and a roll speed of 1 m / min. Roll forming was performed under conditions to obtain a pre-heat conductive sheet having a thickness of 0.5 mm.
- ⁇ Production of laminate> The obtained pre-heat conductive sheet was cut into 6 cm ⁇ 6 cm ⁇ 0.5 mm, 120 sheets were laminated in the thickness direction, and pressed at 120 ° C. for 3 minutes at 0.1 MPa to obtain a laminate having a thickness of about 6 cm.
- Example 2 A heat conductive sheet was produced in the same manner as in Example 1 except that the slice thickness was 250 ⁇ m, the thermal resistance value and tack were measured, and the reworkability was evaluated. The results are shown in Table 1.
- Example 3 Example 1 except that the particulate carbon material was changed to 80 parts by mass of expanded graphite (trade name “EC-500”, manufactured by Ito Graphite Industries Co., Ltd.) having an average particle size of 30 ⁇ m, and the slice thickness was 250 ⁇ m. Thus, a heat conductive sheet was produced, and the thermal resistance value and tack were measured to evaluate the reworkability. The results are shown in Table 1.
- expanded graphite trade name “EC-500”, manufactured by Ito Graphite Industries Co., Ltd.
- Example 4 A heat conductive sheet was produced in the same manner as in Example 1 except that an easily dispersible assembly of carbon nanostructure A as a fibrous carbon material was not added and the slice thickness was 250 ⁇ m, and the thermal resistance value and tack were measured. And reworkability was evaluated. The results are shown in Table 1.
- Example 5 30 parts by mass of particulate carbon material with expanded graphite having an average particle size of 190 ⁇ m (trade name “EC-100”, manufactured by Ito Graphite Industries Co., Ltd.) and expanded graphite having an average particle size of 30 ⁇ m (produced by Ito Graphite Industries, Ltd.) (Trade name “EC-500”) Except for changing to a combination with 20 parts by mass, a heat conductive sheet was produced in the same manner as in Example 1, the thermal resistance value and tack were measured, and reworkability was evaluated. The results are shown in Table 1.
- Example 6 A heat conductive sheet is produced in the same manner as in Example 1 except that the particulate carbon material is changed to 80 parts by mass of expanded graphite (trade name “EC-50” manufactured by Ito Graphite Industries Co., Ltd.) having an average particle size of 250 ⁇ m. Then, the thermal resistance value and tack were measured, and the reworkability was evaluated. The results are shown in Table 1.
- Example 7 90 parts by mass of a normal temperature liquid thermoplastic fluororesin (trade name “DAIEL G-101” manufactured by Daikin Industries, Ltd.) and a normal temperature solid thermoplastic fluororesin (trade name “DAIEL G-912, manufactured by Daikin Industries, Ltd.”) ]) Except having changed into the combination with 10 mass parts, the heat conductive sheet was manufactured similarly to Example 1, the thermal resistance value and the tack were measured, and the rework property was evaluated. The results are shown in Table 1.
- Example 8 A heat conductive sheet was produced in the same manner as in Example 1 except that the number of parts of the particulate carbon material was changed to 30 parts by mass and the slice thickness was 80 ⁇ m, and the thermal resistance value and tack were measured to evaluate the reworkability. . The results are shown in Table 1.
- Comparative Example 1 80 parts by mass of expanded graphite (trade name “EC-100”, average particle size: 190 ⁇ m, manufactured by Ito Graphite Industries Co., Ltd.) as a particulate carbon material, and a room temperature solid thermoplastic fluororesin (Daikin Industries) Using a Hobart mixer (manufactured by Kodaira Manufacturing Co., Ltd., trade name “ACM-5LVT type”) in the presence of 100 parts by weight of ethyl acetate as a solvent. For 5 minutes. The resulting mixture was vacuum degassed for 30 minutes, and ethyl acetate was removed simultaneously with degassing to obtain a composition. The obtained composition was put into a crusher and crushed for 10 seconds. Subsequent procedures other than setting the slice thickness to 250 ⁇ m produced a heat conductive sheet in the same manner as in Example 1, measured the thermal resistance value and tack, and evaluated the reworkability. The results are shown in Table 1.
- Example 2 A heat conductive sheet was produced in the same manner as in Example 1 except that the number of parts of the particulate carbon material was changed to 10 parts by mass and the slice thickness was 80 ⁇ m, and the thermal resistance value and tack were measured to evaluate the reworkability. . The results are shown in Table 1.
- Example 3 The particulate carbon material was changed to 50 parts by mass of artificial graphite (manufactured by Ito Graphite Industry Co., Ltd., trade name “AGB-055”, average particle size: 500 ⁇ m), and the slice thickness was 250 ⁇ m, and the same as in Example 1.
- the heat conductive sheet was manufactured, the thermal resistance value was measured, and the reworkability was evaluated. The results are shown in Table 1.
- the heat conductive sheet of the present invention has excellent handleability and excellent heat conductivity under a relatively low pressure. Therefore, it has excellent workability in manufacturing, maintenance, inspection, repair, etc., excellent durability, and a relatively low pressure.
- a heat dissipating device having excellent heat dissipating characteristics in an additional use environment can be provided.
- the manufacturing method of the heat conductive sheet of this invention can provide the heat conductive sheet which is excellent in handleability and excellent in heat conductivity under a comparatively low pressure.
- the heat radiating device of the present invention can be suitably used in a use environment in which a relatively low pressure is applied between the heat generating body and the heat radiating body.
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Abstract
Description
バルク熱抵抗(m2・K/W)=材料の厚み(m)/材料の熱伝導率(W/m・K)。この関係式から、熱伝導シート自体の熱抵抗、すなわち、熱伝導シートのバルク熱抵抗を小さくするには、熱伝導シートの厚みを薄くすることと、熱伝導シートの熱伝導率を向上させることが必要であると分かる。
一方、熱伝導シートの界面熱抵抗は、発熱体および放熱体との界面における密着性(界面密着性)、発熱体と熱伝導シートのバルク熱抵抗の差、ならびに放熱体と熱伝導シートのバルク熱抵抗の差によって増減することが知られている。特に、界面密着性は、熱伝導シートに加わる圧力、熱伝導シートの硬さ(可撓性)などの影響を受け得る。そこで、熱伝導シートの界面熱抵抗を小さくするため、一般に、熱伝導シート表面にタックを持たせること、または、熱伝導シートの硬度を下げることによって、界面密着性を高めることが考えられてきた。
また、特許文献2の熱伝導シートは、0.1MPaといった比較的低加圧下で熱抵抗が最も低下するが、当該圧力下での0.35℃/Wという熱抵抗の値自体が高く、優れた熱伝導性および放熱特性を示すとはいえない。
また、特許文献3の熱伝導シリコーングリース組成物は、0.15MPaといった比較的低圧領域下で優れた熱伝導性を示すことができるが、シートではなくグリースのため、剥離性が非常に悪く、交換が困難であるなど、リワーク性に劣る。
すなわち、取扱い性と比較的低い圧力下での熱伝導性とに優れる熱伝導シートは存在していなかった。
また、本発明は、比較的低い圧力下で優れた放熱特性を有する放熱装置を提供することを目的とする。
樹脂と、粒子状炭素材料とを含む組成物を加圧してシート状に成形し、プレ熱伝導シートを得る工程と、
該プレ熱伝導シートを厚み方向に複数枚積層して、或いは、該プレ熱伝導シートを折畳または捲回して、積層体を得る工程と、
該積層体を、積層方向に対して45°以下の角度でスライスし、熱伝導シートを得る工程と、を含むことを特徴とする。
このようにして得られた熱伝導シート内では、粒子状炭素材料が厚み方向に配列しており、厚み方向の熱伝導性だけでなく、導電性も高めることができる。
また、本発明によれば、比較的低い圧力下で優れた放熱特性を有する放熱装置を提供することができる。
本発明の熱伝導シートは、例えば、発熱体に放熱体を取り付ける際に発熱体と放熱体との間に挟み込んで使用することができる。即ち、本発明の熱伝導シートは、発熱体と、ヒートシンク、放熱板、放熱フィン等の放熱体と共に放熱装置を構成することができる。そして、本発明の熱伝導シートは、例えば本発明の熱伝導シートの製造方法を用いて製造することができる。
本発明の熱伝導シートは、樹脂と粒子状炭素材料とを含み、0.05MPa加圧下の熱抵抗の値が0.20℃/W以下であることを特徴とする。熱伝導シートが粒子状炭素材料を含有しない場合には、十分な熱伝導性を得ることができない。また、熱伝導シートが樹脂を含有しない場合には、十分な柔軟性が得られない。
ここで、樹脂としては、特に限定されることなく、熱伝導シートの形成に使用され得る既知の樹脂を用いることができるが、中でも熱可塑性樹脂を用いることが好ましい。熱可塑性樹脂を用いれば、使用時(放熱時)の高温環境下で、熱伝導シートの柔軟性を更に向上させ、熱伝導シートを介して発熱体と放熱体とを良好に密着させることができるからである。また、樹脂として、本発明の熱伝導シートの特性及び効果を失わないことを条件として、熱硬化性樹脂を併用することができる。
なお、本発明において、ゴムおよびエラストマーは、「樹脂」に含まれるものとする。
熱伝導シートの形成に使用され得る既知の熱可塑性樹脂としては、常温固体の熱可塑性樹脂、常温液体の熱可塑性樹脂などが挙げられる。本発明の熱伝導シートでは、熱可塑性樹脂として、常温液体の熱可塑性樹脂を用いることが好ましい。ここで、「常温」とは、23℃を指す。常温液体の熱可塑性樹脂を用いると、比較的低い圧力下でも、界面密着性を高めて界面熱抵抗を低下させることができ、熱伝導シートの熱伝導性(すなわち、放熱特性)を向上させることができる。
本発明の熱伝導シートに含有される熱可塑性樹脂は、熱可塑性フッ素樹脂を含むことが好ましく、熱可塑性フッ素樹脂からなることがより好ましい。熱可塑性樹脂として熱可塑性フッ素樹脂を用いることにより、耐熱性、耐油性、および耐薬品性を向上させることができる。また、本発明の熱伝導シートに含有される熱可塑性樹脂は、常温液体の熱可塑性フッ素樹脂であることが更に好ましい。熱可塑性樹脂として常温液体の熱可塑性フッ素樹脂を用いることにより、耐熱性、耐油性、および耐薬品性を向上させることに加え、比較的低い圧力下でも、界面密着性を高めて界面熱抵抗を低下させることができ、熱伝導シートの熱伝導性(すなわち、放熱特性)を向上させることができる。
本発明の熱伝導シートの特性および効果を失わないことを条件として、樹脂として、任意に使用し得る熱硬化性樹脂としては、例えば、天然ゴム;ブタジエンゴム;イソプレンゴム;ニトリルゴム;水素化ニトリルゴム;クロロプレンゴム;エチレンプロピレンゴム;塩素化ポリエチレン;クロロスルホン化ポリエチレン;ブチルゴム;ハロゲン化ブチルゴム;ポリイソブチレンゴム;エポキシ樹脂;ポリイミド樹脂;ビスマレイミド樹脂;ベンゾシクロブテン樹脂;フェノール樹脂;不飽和ポリエステル;ジアリルフタレート樹脂;ポリイミドシリコーン樹脂;ポリウレタン;熱硬化型ポリフェニレンエーテル;熱硬化型変性ポリフェニレンエーテル;などが挙げられる。これらは、1種単独で使用してもよいし、2種以上を併用してもよい。
粒子状炭素材料としては、特に限定されることなく、例えば、人造黒鉛、鱗片状黒鉛、薄片化黒鉛、天然黒鉛、酸処理黒鉛、膨張性黒鉛、膨張化黒鉛などの黒鉛;カーボンブラック;などを用いることができる。これらは、1種単独で使用してもよいし、2種以上を併用してもよい。
中でも、粒子状炭素材料としては、膨張化黒鉛を用いることが好ましい。膨張化黒鉛を使用すれば、熱伝導シートの熱伝導性を向上させることができるからである。
ここで、粒子状炭素材料として好適に使用し得る膨張化黒鉛は、例えば、鱗片状黒鉛などの黒鉛を硫酸などで化学処理して得た膨張性黒鉛を、熱処理して膨張させた後、微細化することにより得ることができる。そして、膨張化黒鉛としては、例えば、伊藤黒鉛工業株式会社製のEC1500、EC1000、EC500、EC300、EC100、EC50(いずれも商品名)等が挙げられる。
ここで、本発明の熱伝導シートに含有されている粒子状炭素材料の平均粒子径は、0.1μm以上であることが好ましく、1μm以上であることがより好ましく、25μm以上であることが更に好ましく、300μm以下であることが好ましく、250μm以下であることがより好ましく、200μm以下であることが更に好ましい。粒子状炭素材料の平均粒子径が上記範囲内であれば、熱伝導シートの硬さおよび粘着性のバランスをより向上させて取扱い性を向上させることができるとともに、熱伝導シートの熱抵抗をより低下させて熱伝導性を向上させることができるからである。
また、本発明の熱伝導シートに含有されている粒子状炭素材料のアスペクト比(長径/短径)は、1以上10以下であることが好ましく、1以上5以下であることがより好ましい。
そして、本発明の熱伝導シート中の粒子状炭素材料の含有割合は、樹脂100質量部に対して、20質量部以上であることが好ましく、30質量部以上であることがより好ましく、50質量部以上であることが更に好ましく、150質量部以下であることが好ましく、90質量部以下であることがより好ましく、80質量部以下であることが更に好ましい。熱伝導シート中の粒子状炭素材料の含有割合が、樹脂100質量部に対して、20質量部以上150質量部以下であれば、熱伝導シートの硬さと粘着性とのバランスを一層向上させることができ、取扱い性を一層向上させることができる。また、粒子状炭素材料の含有割合が、樹脂100質量部に対して、20質量部以上であれば、熱伝導シートの熱伝導率を向上させることができる。また、粒子状炭素材料の含有割合が、樹脂100質量部に対して、150質量部以下であれば、熱伝導シートの粘着性を向上させ、粒子状炭素材料の粉落ちを十分に防止することができる。
本発明の熱伝導シートは、任意に繊維状炭素材料を含有してもよい。任意に含有される繊維状炭素材料としては、特に限定されることなく、例えば、カーボンナノチューブ、気相成長炭素繊維、有機繊維を炭化して得られる炭素繊維、およびそれらの切断物などを用いることができる。これらは、1種単独で使用してもよいし、2種以上を併用してもよい。
そして、本発明の熱伝導シートに繊維状炭素材料を含有させれば、熱伝導性を更に向上させることができると共に、粒子状炭素材料の粉落ちを防止することもできる。なお、繊維状炭素材料を配合することで粒子状炭素材料の粉落ちを防止することができる理由は、明らかではないが、繊維状炭素材料が三次元網目構造を形成することにより、熱伝導性や強度を高めつつ粒子状炭素材料の脱離を防止しているためであると推察される。
ここで、繊維状炭素材料として好適に使用し得る、カーボンナノチューブを含む繊維状の炭素ナノ構造体は、カーボンナノチューブ(以下、「CNT」と称することがある。)のみからなるものであってもよいし、CNTと、CNT以外の繊維状の炭素ナノ構造体との混合物であってもよい。
なお、繊維状の炭素ナノ構造体中のCNTとしては、特に限定されることなく、単層カーボンナノチューブおよび/または多層カーボンナノチューブを用いることができるが、CNTは、単層から5層までのカーボンナノチューブであることが好ましく、単層カーボンナノチューブであることがより好ましい。単層カーボンナノチューブを使用すれば、多層カーボンナノチューブを使用した場合と比較し、本発明の熱伝導シートの熱伝導性および強度を更に向上させることができるからである。
なお、「繊維状の炭素ナノ構造体の平均直径(Av)」および「繊維状の炭素ナノ構造体の直径の標準偏差(σ:標本標準偏差)」は、それぞれ、透過型電子顕微鏡を用いて無作為に選択した繊維状の炭素ナノ構造体100本の直径(外径)を測定して求めることができる。そして、CNTを含む繊維状の炭素ナノ構造体の平均直径(Av)および標準偏差(σ)は、CNTを含む繊維状の炭素ナノ構造体の製造方法や製造条件を変更することにより調整してもよいし、異なる製法で得られたCNTを含む繊維状の炭素ナノ構造体を複数種類組み合わせることにより調整してもよい。
なお、本発明において、「BET比表面積」とは、BET法を用いて測定した窒素吸着比表面積を指す。
そして、熱伝導シートに含まれうる繊維状炭素材料の平均繊維径は、1nm以上であることが好ましく、3nm以上であることがより好ましく、2μm以下であることが好ましく、1μm以下であることがより好ましい。繊維状炭素材料の平均繊維径が上記範囲内であれば、熱伝導シートの熱伝導性、柔軟性および強度を十分に高いレベルで並立させることができるからである。ここで、繊維状炭素材料のアスペクト比は、10を超えることが好ましい。
そして、本発明の熱伝導シート中の繊維状炭素材料の含有割合は、0.05質量%以上であることが好ましく、0.2質量%以上であることがより好ましく、5質量%以下であることが好ましく、3質量%以下であることがより好ましい。熱伝導シート中の繊維状炭素材料の含有割合が0.05質量%以上であれば、熱伝導シートの熱伝導性および強度を十分に向上させることができると共に、粒子状炭素材料の粉落ちを十分に防止することができるからである。更に、熱伝導シート中の繊維状炭素材料の含有割合が5質量%以下であれば、繊維状炭素材料の配合により熱伝導シートの硬度が上昇する(即ち、柔軟性が低下する)のを抑制して、本発明の熱伝導シートの熱伝導性および柔軟性を十分に高いレベルで並立させることができるからである。
本発明の熱伝導シートには、必要に応じて、熱伝導シートの形成に使用され得る既知の添加剤を配合することができる。そして、熱伝導シートに配合し得る添加剤としては、特に限定されることなく、例えば、脂肪酸エステルなどの可塑剤;赤りん系難燃剤、りん酸エステル系難燃剤などの難燃剤;ウレタンアクリレートなどの靭性改良剤;酸化カルシウム、酸化マグネシウムなどの吸湿剤;シランカップリング剤、チタンカップリング剤、酸無水物などの接着力向上剤;ノニオン系界面活性剤、フッ素系界面活性剤などの濡れ性向上剤;無機イオン交換体などのイオントラップ剤;等が挙げられる。
そして、本発明の熱伝導シートは、特に限定されることなく、以下の性状を有していることが好ましい。
本発明の熱伝導シートは、0.05MPa加圧下の熱抵抗の値が0.20℃/W以下であり、0.19℃/W以下であることがより好ましく、0.17℃/W以下であることが更に好ましい。0.05MPa加圧下の熱抵抗の値が0.20℃/W以下であると、比較的低い圧力が加えられる使用環境下で、優れた熱伝導性を有することができる。
ここで、熱抵抗の値は、熱伝導シートの熱抵抗を測定するのに通常用いられる既知の測定方法を用いて測定することができ、樹脂材料熱抵抗試験器(例えば、日立テクノロジーアンドサービス社製、商品名「C47108」)などで測定することができる。
尚、加圧力を0.5MPaから0.05MPaへ低下させたときの熱抵抗値の変化率は、次式で算出することができる:100×(0.05MPa加圧下での熱抵抗値-0.5MPa加圧下での熱抵抗値)/0.5MPa加圧下での熱抵抗値(%)。
本発明の熱伝導シートは、プローブタック試験で測定したタックが1.40N以下であることが好ましく、1.30N以下であることがより好ましく、1.20N以下であることが更に好ましい。「タック」とは、JIS Z0109:2015で規定される通り、軽い力で短時間に被着体に接着する特性を意味し、本明細書中では「接着性」とも称する。本発明の熱伝導シートのタックは、プローブタック試験で測定される。具体的には、25℃の温度条件で、φ10mmの平らなプローブを荷重0.5Nの圧力を加えながら測定対象の熱伝導シートに10秒間押し付けた後、プローブを該熱伝導シートから引き離すときに要する力として測定される。プローブタック試験で測定したタックが1.40N以下であると、使用時には良好な密着性を示しつつ、取り付け時および交換時に良好な剥離性を有し、発熱体や放熱体などの取付物から、熱伝導シートを破壊することなく、すなわち、当該取付物に熱伝導シート成分を残存させることなく、熱伝導シートを取り外すことができる。言い換えると、プローブタック試験で測定したタックの数値が小さい程、取扱い性に優れる。
なお、本発明の熱伝導シートのタックは、プローブタック試験機(例えば、株式会社レスカ製、商品名「TAC1000」)などで測定することができる。
本発明の熱伝導シートは、25℃でのアスカーC硬度が、60以上であり、65以上であることが好ましく、70以上であることがより好ましい。25℃でのアスカーC硬度が60以上であれば、室温で適度な硬さを有することができ、取り付け時及び交換時の作業性を良好なものとすることができる。
また、本発明の熱伝導シートは、25℃でのアスカーC硬度が、80以下であることが好ましく、70以下であることがより好ましい。25℃でのアスカーC硬度が80以下であれば、室温環境下で十分な粘着性を有することができ、取り付け時及び交換時の作業性をより向上させることができる。
また、本発明の熱伝導シートは、70℃でのアスカーC硬度が、70以下であることが好ましく、65以下であることがより好ましい。70℃でのアスカーC硬度が70以下であれば、使用時(放熱時)の高温環境下で界面密着性をより向上させることができ、熱伝導性をより向上させることができる。
熱伝導シートは、厚み方向の熱伝導率が、25℃において、20W/m・K以上であることが好ましく、30W/m・K以上であることがより好ましく、40W/m・K以上であることが更に好ましい。熱伝導率が20W/m・K以上であれば、例えば熱伝導シートを発熱体と放熱体との間に挟み込んで使用した場合に、発熱体から放熱体へと熱を効率的に伝えることができる。
熱伝導シートの厚みは、好ましくは0.05mm(50μm)~10mmである。本発明の熱伝導シートは、取扱い性を損なわない限りにおいて、厚みを薄くする程、熱伝導シートのバルク熱抵抗を小さくすることができ、熱伝導性および放熱装置に使用した場合の放熱特性を向上させることができる。
さらに、本発明の熱伝導シートは、密度が1.8g/cm3以下であることが好ましく、1.6g/cm3以下であることがより好ましい。このような熱伝導シートは、汎用性が高く、例えば電子部品などの製品に実装した際に、かかる電子部品の軽量化に寄与することができるからである。
[プレ熱伝導シート成形工程]
プレ熱伝導シート成形工程では、樹脂および粒子状炭素材料を含み、任意に繊維状炭素材料および/または添加剤を更に含有する組成物を加圧してシート状に成形し、プレ熱伝導シートを得る。
ここで、組成物は、樹脂および粒子状炭素材料と、任意の繊維状炭素材料および/または添加剤とを混合して調製することができる。そして、樹脂、粒子状炭素材料、繊維状炭素材料および添加剤としては、本発明の熱伝導シートに含まれ得る樹脂、粒子状炭素材料、繊維状炭素材料および添加剤として上述したものを用いることができる。因みに、熱伝導シートの樹脂を架橋型の樹脂とする場合には、架橋型の樹脂を含む組成物を用いてプレ熱伝導シートを形成してもよいし、架橋可能な樹脂と硬化剤とを含有する組成物を用いてプレ熱伝導シートを形成し、プレ熱伝導シート成形工程後に架橋可能な樹脂を架橋させることにより、熱伝導シートに架橋型の樹脂を含有させてもよい。
そして、上述のようにして調製した組成物は、任意に脱泡および解砕した後に、加圧してシート状に成形することができる。なお、混合時に溶媒を用いている場合には、溶媒を除去してからシート状に成形することが好ましく、例えば真空脱泡を用いて脱泡を行えば、脱泡時に溶媒の除去も同時に行うことができる。
そして、組成物を加圧してシート状に成形してなるプレ熱伝導シートでは、粒子状炭素材料が主として面内方向に配列し、特にプレ熱伝導シートの面内方向の熱伝導性が向上すると推察される。
なお、プレ熱伝導シートの厚みは、特に限定されることなく、例えば0.05mm以上2mm以下とすることができる。また、熱伝導シートの熱伝導性を更に向上させる観点からは、プレ熱伝導シートの厚みは、粒子状炭素材料の平均粒子径の20倍超5000倍以下であることが好ましい。
積層体形成工程では、プレ熱伝導シート成形工程で得られたプレ熱伝導シートを厚み方向に複数枚積層して、或いは、プレ熱伝導シートを折畳または捲回して、積層体を得る。ここで、プレ熱伝導シートの折畳による積層体の形成は、特に限定されることなく、折畳機を用いてプレ熱伝導シートを一定幅で折り畳むことにより行うことができる。また、プレ熱伝導シートの捲回による積層体の形成は、特に限定されることなく、プレ熱伝導シートの短手方向または長手方向に平行な軸の回りにプレ熱伝導シートを捲き回すことにより行うことができる。
更に、プレ熱伝導シートの表面に設ける接着層としては、特に限定されることなく、両面テープなどを用いることができる。
スライス工程では、積層体形成工程で得られた積層体を、積層方向に対して45°以下の角度でスライスし、積層体のスライス片よりなる熱伝導シートを得る。ここで、積層体をスライスする方法としては、特に限定されることなく、例えば、マルチブレード法、レーザー加工法、ウォータージェット法、ナイフ加工法等が挙げられる。中でも、熱伝導シートの厚みを均一にし易い点で、ナイフ加工法が好ましい。また、積層体をスライスする際の切断具としては、特に限定されることなく、スリットを有する平滑な盤面と、このスリット部より突出した刃部とを有するスライス部材(例えば、鋭利な刃を備えたカンナやスライサー)を用いることができる。
刃部を備える1枚の刃は、刃先の表裏両側が切刃となっている「両刃」であってもよく、刃の表側のみが切刃となっている「片刃」であってもよい。刃先1の断面図である図1~4を参照すると、両刃は左右両側が切刃2,3となっており(図1~3)、片刃は左右のうち表側に相当する片側のみが切刃2となっている(図4)。
図9(a),9(b)に例示するように、2枚刃は、1枚の表刃17と1枚の裏刃18とで構成され、表刃17と裏刃18とは刀身同士が接触して配置される。切削の際に、切削対象物に近い側に位置する刃が表刃17であり、切削対象物から遠い方の刃が裏刃18である。表刃と裏刃は、当該2枚刃が刃として機能を果たす(すなわち、切削機能を有する)限りにおいて、スリット部から突出した刃先の最先端同士の高さが、同じでも異なってもよい(すなわち、揃っていても、上下にずれていてもよい)。
例えば、図9(a)は、表刃17と裏刃18双方が片刃であり、互いに峰側同士で接触し、裏刃の刃先の最先端が表刃の刃先の最先端より低く(すなわち、下に)ずれて配置された2枚刃の一実施形態である。また、図9(b)は、表刃17が片刃で裏刃18が両刃であり、表刃が峰側で裏刃と接触し、裏刃の刃先の最先端が表刃の刃先の最先端より低く(すなわち、下に)ずれて配置された2枚刃の一実施形態である。
また、2枚の刃のうちの一方または両方の刃が両刃の場合、当該両刃は、対称刃であっても非対称刃であってもよい。
また、2枚の刃は、それぞれ、1段刃であっても2段刃であってもよい。
本発明の製造方法に従って製造した熱伝導シートは、熱伝導性、強度、導電性に優れている。従って、複合材料シートおよび熱伝導シートは、例えば、各種機器および装置などにおいて使用される放熱材料、放熱部品、冷却部品、温度調節部品、電磁波シールド部材、電磁波吸収部材、被圧着物を加熱圧着する場合に被圧着物と加熱圧着装置との間に介在させる熱圧着用ゴムシートとして好適である。
ここで、各種機器および装置などとしては、特に限定されることなく、サーバー、サーバー用パソコン、デスクトップパソコン等の電子機器;ノートパソコン、電子辞書、PDA、携帯電話、ポータブル音楽プレイヤー等の携帯電子機器;液晶ディスプレイ(バックライトを含む)、プラズマディスプレイ、LED、有機EL、無機EL、液晶プロジェクタ、時計等の表示機器;インクジェットプリンタ(インクヘッド)、電子写真装置(現像装置、定着装置、ヒートローラ、ヒートベルト)等の画像形成装置;半導体素子、半導体パッケージ、半導体封止ケース、半導体ダイボンディング、CPU、メモリ、パワートランジスタ、パワートランジスタケース等の半導体関連部品;リジッド配線板、フレキシブル配線板、セラミック配線板、ビルドアップ配線板、多層基板等の配線基板(配線板にはプリント配線板なども含まれる);真空処理装置、半導体製造装置、表示機器製造装置等の製造装置;断熱材、真空断熱材、輻射断熱材等の断熱装置;DVD(光ピックアップ、レーザー発生装置、レーザー受光装置)、ハードディスクドライブ等のデータ記録機器;カメラ、ビデオカメラ、デジタルカメラ、デジタルビデオカメラ、顕微鏡、CCD等の画像記録装置;充電装置、リチウムイオン電池、燃料電池等のバッテリー機器等が挙げられる。
本発明の放熱装置は、本発明の熱伝導シートを発熱体と放熱体の間に介在させてなることを特徴とする。本発明の放熱装置の使用温度は、250℃を超えないことが好ましく、-20~200℃の範囲であるのがより好ましい。使用温度が250℃を超えると、樹脂成分の柔軟性が急激に低下し、放熱特性が低下する場合があるからである。当該使用温度の発熱体としては、例えば、半導体パッケージ、ディスプレイ、LED、電灯等が挙げられる。
実施例および比較例において、熱伝導シートの熱抵抗、およびリワーク性は、それぞれ以下の方法を使用して測定または評価した。
<熱抵抗値>
熱伝導シートの熱抵抗値の測定は、樹脂材料熱抵抗試験器(株式会社日立テクノロジーアンドサービス製、商品名「C47108」)を使用した。試料サイズは1cm角に切り出し、一定の圧力を加えた時の熱抵抗値を測定した。試料温度は50℃になるように測定を行った。熱抵抗値が小さい程、熱伝導性に優れ、発熱体と放熱体との間に介在させて放熱装置とする際の放熱特性に優れていることを示す。
加圧する圧力は0.05MPaと0.50MPaの2点で評価を行った。
また、加圧力を0.5MPaから0.05MPaへ低下させたときの熱抵抗値の変化率を「圧力低下による熱抵抗変化率(%)」として算出した。圧力低下による熱抵抗変化率は、次式で算出することができる:100×(0.05MPa加圧下での熱抵抗値-0.5MPa加圧下での熱抵抗値)/0.5MPa加圧下での熱抵抗値(%)。加圧力を低下させると熱抵抗値は増加し、その圧力低下による熱抵抗の変化率(増加率)が小さいほど、熱伝導シートが硬く、取扱い性に優れることを示す。
アルミ板に熱伝導シートのサンプル(10mm×10mm)を貼付け、当該サンプル上で0.1kgロールを5往復させて荷重をかけた。次いでサンプルをアルミ板から剥がす作業を実施して、サンプルの状態を評価した。この試験を同じ手順で3回繰り返して、以下の通りに評価した。結果を表1に示す。
非常に良好:3回ともサンプルに千切れなく剥がすことができ再度の使用が可能であった。
良好:2回はサンプルに千切れなく剥がすことができ再度の使用が可能であったが、1回は千切れが発生した。
劣る:3回ともサンプルを剥がすことができず再使用が不可能であった。
熱伝導シートのタックの測定は、プローブタック試験機(株式会社レスカ製、商品名「TAC1000」)を使用した。φ10mmのフラットな形状のプローブ先端を0.5N(50gf)の荷重で樹脂シートに10s間押付け、プローブを樹脂シートから引き離す時に要する力を測定した。測定温度は25℃とした。タックの測定値が小さいほど、粘着性が低く、取扱い性に優れることを示す。
尚、柔らかすぎてプローブから取り外すことが不可能な場合は、「測定不能」と評価した。
国際公開第2006/011655号の記載に従って、スーパーグロース法によってSGCNTを含む繊維状の炭素ナノ構造体Aを得た。
得られた繊維状の炭素ナノ構造体Aは、G/D比が3.0、BET比表面積が800m2/g、質量密度が0.03g/cm3であった。また、透過型電子顕微鏡を用い、無作為に選択した100本の繊維状の炭素ナノ構造体Aの直径を測定した結果、平均直径(Av)が3.3nm、直径の標本標準偏差(σ)に3を乗じた値(3σ)が1.9nm、それらの比(3σ/Av)が0.58、平均長さが100μmであった。また、得られた繊維状の炭素ナノ構造体Aは、主に単層CNT(「SGCNT」とも称する)により構成されていた。
<分散液の調製>
繊維状炭素材料としての繊維状の炭素ナノ構造体Aを400mg量り取り、溶媒としてのメチルエチルケトン2L中に混ぜ、ホモジナイザーにより2分間撹拌し、粗分散液を得た。湿式ジェットミル(株式会社常光製、商品名「JN-20」)を使用し、得られた粗分散液を湿式ジェットミルの0.5mmの流路に100MPaの圧力で2サイクル通過させて、繊維状炭素ナノ構造体Aをメチルエチルケトンに分散させた。そして、固形分濃度0.20質量%の分散液Aを得た。
<溶媒の除去>
その後、得られた分散液Aをキリヤマろ紙(No.5A)を用いて減圧ろ過し、シート状の易分散性集合体を得た。
<組成物の調製>
繊維状炭素材料としての炭素ナノ構造体Aの易分散性集合体を0.1質量部と、粒子状炭素材料としての膨張化黒鉛(伊藤黒鉛工業株式会社製、商品名「EC-100」、平均粒子径:190μm)を50質量部と、樹脂としての常温液体の熱可塑性フッ素樹脂(ダイキン工業株式会社製、商品名「ダイエルG―101」)100質量部とをホバートミキサー(株式会社小平製作所製、商品名「ACM-5LVT型」、容量:5L)で80℃に加温し、30分間混合した。混合して得られた組成物をワンダークラッシュミル(大阪ケミカル株式会社製、商品名「D3V-10」)に投入して、1分間解砕した。
次いで、解砕した組成物5gを、サンドブラスト処理を施した厚さ50μmのPETフィルム(保護フィルム)で挟み、ロール間隙550μm、ロール温度50℃、ロール線圧50kg/cm、ロール速度1m/分の条件にて圧延成形し、厚さ0.5mmのプレ熱伝導シートを得た。
<積層体の作製>
得られたプレ熱伝導シートを6cm×6cm×0.5mmに裁断し、厚み方向に120枚積層し、120℃で3分間、0.1MPaでプレスし厚さ約6cmの積層体を得た。
その後、プレ熱伝導シートの積層体の積層断面を、0.3MPaの圧力で押し付けながら、木工用スライサー(株式会社丸仲鐵工所製、商品名「超仕上げかんな盤スーパーメカS」を用いて、積層方向に対して0度の角度でスライス(換言すれば、積層されたプレ熱伝導シートの主面の法線方向にスライス)し、縦6cm×横6cm×厚さ150μmの熱伝導シートを得た。木工用スライサーのナイフは、2枚の片刃が、切刃の反対側同士で接触し、表刃の刃先の最先端が裏刃の刃先の最先端よりも0.5mm高くスリット部からの突出長さ0.11mmに配置され、表刃の刃角21°である2枚刃のものを用いた。
得られた熱伝導シートについて、上記評価方法に従って、熱抵抗値およびタックを測定し、リワーク性を評価した。結果を表1に示す。
スライス厚みを250μmとした以外は実施例1と同様にして熱伝導シートを製造し、熱抵抗値およびタックを測定し、リワーク性を評価した。結果を表1に示す。
粒子状炭素材料を平均粒子径が30μmの膨張化黒鉛(伊藤黒鉛工業株式会社製、商品名「EC-500」)80質量部に変更し、スライス厚みを250μmとした以外は実施例1と同様にして熱伝導シートを製造し、熱抵抗値およびタックを測定し、リワーク性を評価した。結果を表1に示す。
繊維状炭素材料としての炭素ナノ構造体Aの易分散性集合体を加えず、スライス厚みを250μmとした以外は実施例1と同様にして熱伝導シートを製造し、熱抵抗値およびタックを測定し、リワーク性を評価した。結果を表1に示す。
粒子状炭素材料を平均粒子径が190μmの膨張化黒鉛(伊藤黒鉛工業株式会社製、商品名「EC-100」)30質量部および平均粒子径が30μmの膨張化黒鉛(伊藤黒鉛工業株式会社製、商品名「EC-500」)20質量部との組み合わせに変更した以外は実施例1と同様にして熱伝導シートを製造し、熱抵抗値およびタックを測定し、リワーク性を評価した。結果を表1に示す。
粒子状炭素材料を平均粒子径が250μmの膨張化黒鉛(伊藤黒鉛工業株式会社製、商品名「EC-50」)80質量部に変更した以外は実施例1と同様にして熱伝導シートを製造し、熱抵抗値およびタックを測定し、リワーク性を評価した。結果を表1に示す。
樹脂を常温液体の熱可塑性フッ素樹脂(ダイキン工業株式会社製、商品名「ダイエルG―101」)90質量部と常温固体の熱可塑性フッ素樹脂(ダイキン工業株式会社製、商品名「ダイエルG―912」)10質量部との組み合わせに変更した以外は実施例1と同様にして熱伝導シートを製造し、熱抵抗値およびタックを測定し、リワーク性を評価した。結果を表1に示す。
粒子状炭素材料の部数を30質量部に変更し、スライス厚みを80μmとした以外は実施例1と同様にして熱伝導シートを製造し、熱抵抗値およびタックを測定し、リワーク性を評価した。結果を表1に示す。
粒子状炭素材料としての膨張化黒鉛(伊藤黒鉛工業株式会社製、商品名「EC-100」、平均粒子径:190μm)80質量部と、樹脂としての常温固体の熱可塑性フッ素樹脂(ダイキン工業株式会社製、商品名「ダイエルG―912」)100質量部とを、溶媒としての酢酸エチル100質量部の存在下においてホバートミキサー(株式会社小平製作所製、商品名「ACM-5LVT型」)を用いて5分攪拌混合した。得られた混合物を30分真空脱泡し、脱泡と同時に酢酸エチルの除去を行って組成物を得た。得られた組成物を解砕機に投入し、10秒間解砕した。スライス厚みを250μmとした以外の以降の手順は実施例1と同様にして熱伝導シートを製造し、熱抵抗値およびタックを測定し、リワーク性を評価した。結果を表1に示す。
粒子状炭素材料の部数を10質量部に変更し、スライス厚みを80μmとした以外は実施例1と同様にして熱伝導シートを製造し、熱抵抗値およびタックを測定し、リワーク性を評価した。結果を表1に示す。
粒子状炭素材料を人造黒鉛(伊藤黒鉛工業株式会社製、商品名「AGB―055」、平均粒子径:500μm)50質量部に変更し、スライス厚みを250μmとした以外は実施例1と同様にして熱伝導シートを製造し、熱抵抗値を測定し、リワーク性を評価した。結果を表1に示す。
熱伝導シートに替えて、熱伝導性シリコーン組成物としての市販品のシリコーングリース(信越化学工業株式会社製、商品名「G―751」)を用いて、測定を行った。結果を表1に示す。
2.切刃
3.切刃
4.中心軸
5.刃角
6.峰
7.刃全体
8.表
9.裏
10.刃高
11.刃厚
12.刃幅
13.垂線
14.基準線
15.垂線
16.刃角
17.表刃
18.裏刃
Claims (8)
- 樹脂と粒子状炭素材料とを含み、0.05MPa加圧下の熱抵抗の値が0.20℃/W以下である、熱伝導シート。
- 加圧力を0.50MPaから0.05MPaへ変化させたときの熱抵抗値の変化率が+150.0%以下である、請求項1に記載の熱伝導シート。
- プローブタック試験で測定したタックが1.40N以下である、請求項1又は2に記載の熱伝導シート。
- 前記樹脂100質量部に対し、前記粒子状炭素材料が20質量部以上である、請求項1~3のいずれか1項に記載の熱伝導シート。
- 前記樹脂が熱可塑性樹脂である、請求項1~4のいずれか1項に記載の熱伝導シート。
- 前記熱可塑性樹脂が常温液体の熱可塑性樹脂である、請求項5に記載の熱伝導シート。
- 発熱体と放熱体との間に請求項1~6のいずれか1項に記載の熱伝導シートを介在させてなる、放熱装置。
- 樹脂と、粒子状炭素材料とを含む組成物を加圧してシート状に成形し、プレ熱伝導シートを得る工程と、
該プレ熱伝導シートを厚み方向に複数枚積層して、或いは、該プレ熱伝導シートを折畳または捲回して、積層体を得る工程と、
該積層体を、積層方向に対して45°以下の角度でスライスし、熱伝導シートを得る工程と、
を含む、熱伝導シートの製造方法。
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