WO2007126133A1 - 炭素繊維複合シート - Google Patents
炭素繊維複合シート Download PDFInfo
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- WO2007126133A1 WO2007126133A1 PCT/JP2007/059426 JP2007059426W WO2007126133A1 WO 2007126133 A1 WO2007126133 A1 WO 2007126133A1 JP 2007059426 W JP2007059426 W JP 2007059426W WO 2007126133 A1 WO2007126133 A1 WO 2007126133A1
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- carbon fiber
- composite sheet
- fiber composite
- resin component
- silicone resin
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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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
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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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
- C08J5/241—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres
- C08J5/243—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using inorganic fibres using carbon fibres
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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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- 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
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/24—Thermosetting resins
-
- 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
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
-
- 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
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
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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
- C08K2201/004—Additives being defined by their length
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
- Y10T428/249928—Fiber embedded in a ceramic, glass, or carbon matrix
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
- Y10T428/24994—Fiber embedded in or on the surface of a polymeric matrix
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/269—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension including synthetic resin or polymer layer or component
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2918—Rod, strand, filament or fiber including free carbon or carbide or therewith [not as steel]
Definitions
- the present invention relates to a carbon fiber composite sheet in which pitch-based carbon fibers and a thermosetting resin component are combined.
- High-performance carbon fibers can be classified into PAN-based carbon fibers made from polyacrylonitrile (P A N) and pitch-based carbon fibers made from a series of pitches.
- PAN-based carbon fibers made from polyacrylonitrile (P A N)
- pitch-based carbon fibers made from a series of pitches.
- Carbon fiber is used widely in aerospace / space applications, architecture / civil engineering applications, sports / leisure applications, etc., taking advantage of the fact that its strength and elastic modulus are significantly higher than those of ordinary synthetic polymers.
- Carbon fibers have a higher thermal conductivity than ordinary synthetic polymers, but further improvements in thermal conductivity are being investigated.
- the thermal conductivity of commercially available PAN-based carbon fibers is usually less than 20 O W / (m ⁇ K) ′ and is not necessarily suitable from the viewpoint of thermal management.
- pitch-based carbon fibers are recognized as achieving high thermal conductivity compared to PAN-based carbon fibers because of their high graphitization properties!
- thermally conductive filler aluminum oxide boron nitride, nitrogen It is known to be filled with metal oxides such as aluminum, magnesium oxide, zinc oxide, silicon carbide, quartz, and aluminum oxide, metal nitride, metal carbide, and metal hydroxide.
- metal-based fillers have a high specific gravity and become heavy when used as a composite material.
- a spherical material such as carbon black, which is a carbon-based material, causes so-called powder falling when the addition amount is high, and particularly in an electronic device, its conductivity adversely affects the device.
- carbon fiber has the advantage of reducing the weight of the composite material when it is added in the same volume as the filler of the metal material type due to its small specific gravity, and because the shape is fibrous, There is also a merit that the powder does not easily fall off.
- the composite material may be used as a connection between a heating element and a heat sink.
- a highly rigid resin composition is used, a gap may be formed between the heating element and the heat sink, and efficient heat conduction cannot be achieved. Therefore, it was desired for the composite material to be more flexible and to have high followability on the surfaces of the heating element and the heat sink.
- the carbon fiber forms a network in a state where some matrix is interposed.
- the network is formed three-dimensionally, high heat conduction of the carbon fiber is achieved not only in the in-plane direction of the molded body but also in the thickness direction. It is considered to be appropriate.
- the thermal conductivity in the thickness direction is improved by the formation of the carbon fiber network. Because I can't do it enough It was difficult to say that it was good.
- Patent Document 1 discloses a heat conductive molded article having high mechanical strength in which carbon fibers aligned in one direction are impregnated with graphite powder and a thermosetting resin.
- Patent Document 2 discloses that improving the physical properties of carbon fiber improves physical properties such as thermal conductivity, and it is unclear about the clear improvement in the thermal properties of the force-molded body.
- Patent Document 1 Japanese Patent Application Laid-Open No. 5-1 7 5 9 3
- Patent Document 2 Japanese Patent Laid-Open No. 2-2 4 2 9 1 9 Disclosure of Invention
- An object of the present invention is to provide a carbon fiber composite sheet that solves the problems that the prior art cannot achieve and exhibits appropriate thermal conductivity.
- the object is to provide a thermosetting resin component selected from the group consisting of a thermosetting silicone gel component, a thermosetting epoxy resin component, and a thermosetting silicone resin component, and a carbon fiber assembly.
- a thermosetting resin component selected from the group consisting of a thermosetting silicone gel component, a thermosetting epoxy resin component, and a thermosetting silicone resin component, and a carbon fiber assembly.
- a carbon fiber composite sheet obtained by curing the thermosetting resin component and having a crystallite size of 5 derived from the growth direction of the hexagonal network surface of the carbon fibers constituting the carbon fiber aggregate. It can be achieved by a carbon fiber composite sheet that is at least nm and the thermal conductivity of the carbon fiber composite sheet is 2 W / (m ⁇ K) or more.
- Examples of the raw material for the carbon aggregate used in the present invention include condensed polycyclic hydrocarbon compounds such as naphthalene and phenanthrene, petroleum pitch and stone.
- Examples thereof include condensed heterocyclic compounds such as a carbon-based pitch.
- condensed polycyclic hydrocarbon compounds such as naphthalenes and phenanthrenes are preferable, and optically anisotropic pitch, that is, mesophase pitch is particularly preferable.
- mesophase pitch is particularly preferable.
- the softening point of the raw material pitch can be obtained by a Mettler method, and is preferably from 2550 ° C to 3500 ° C.
- the softening point is lower than 250 ° C., great heat shrinkage occurs if the fibers are fused to each other at the time of infusibilization.
- the temperature is higher than 350 ° C, the pitch is thermally decomposed and is not easily formed into a filament.
- the raw material pitch is spun by a melt blow method, and then infusibilized and fired to form a carbon fiber aggregate.
- a melt blow method for spinning the raw material of the carbon fiber
- the ratio of the nozzle hole length to the hole diameter is smaller than 3 is preferably used. More preferably, it is smaller than 1.5.
- the temperature of the nozzle during spinning is not particularly limited, and the temperature at which a stable spinning state can be maintained, that is, the viscosity of the spinning pitch is 2 to 80 Pa ⁇ S, preferably 30 to 6 OP a ⁇ S. Any temperature is acceptable.
- the pitch fiber discharged from the nozzle hole is blown near the thinning point with a gas having a linear velocity of 100 to 100 000 Om per minute heated to 100 to 350 ° C. Short fiber.
- Short fiber As the gas to be blown, air, nitrogen, or argon can be used, but air is preferable from the viewpoint of cost performance.
- the shortened pitch fibers are collected on a wire mesh belt and continuously pine. It becomes a toroidal shape and is further cross-wrapped to form a carbon fiber aggregate.
- the carbon fiber aggregate is preferably a mat in which the carbon fibers are three-dimensionally entangled inside the carbon fiber aggregate. When the carbon fiber aggregate is such a fiber aggregate, The three-dimensional thermal conductivity is even better.
- Such entanglement can be achieved in a cylinder called chimji while reaching the wire mesh belt from the spinning nozzle.
- the aggregate made of pitch fibers thus obtained is infusibilized by a known method and fired at 15500 to 35500C. Infusibilization can be performed at 200 to 350 ° C using gas with air, or ozone, nitrogen dioxide, nitrogen, oxygen, iodine, bromine added to air. Considering convenience, it is preferable to carry out in air.
- the infusible pitch fibers are fired in vacuum or in an inert gas such as nitrogen, argon, krypton, etc., but at normal pressure and at low cost.
- the firing temperature is preferably 2300 to 3500 ° C in order to increase the thermal conductivity of the carbon fiber. More preferably, it is 2500 to 3500 ° C.
- the crucible made of graphite is not limited in size and shape as long as the desired amount of the infusible mat used as the above raw material can be added, but it does not oxidize in the furnace during firing or cooling.
- a highly airtight one with a lid can be suitably used.
- the carbon fiber constituting the carbon fiber aggregate used in the present invention needs to have a crystallite size derived from the growth direction of the hexagonal network surface of 5 nm or more.
- the crystallite size derived from the growth direction of the hexagonal mesh surface is obtained by a known method. It can be obtained from the diffraction line from the (1 1 0) plane of the carbon crystal obtained by the X-ray diffraction method.
- the reason why the crystallite size is important is that heat conduction is mainly performed by phonon, and it is crystal that generates phonon.
- the crystallite size is more preferably 20 nm or more, and further preferably 30 nm or more.
- the carbon fiber aggregate is made of carbon fibers made from Mesofunez pitch, the average fiber diameter of the carbon fibers is 5 to 20 ⁇ , and the average fiber diameter length is 0.001 to 100 Omm. It is preferable.
- the average fiber diameter is more preferably 3 to 15 ⁇ , and still more preferably 5 to 12 / m.
- the average fiber length is more preferably from 0.1 to 500 mm, and more preferably from 3 to 30 Omm.
- the CV value obtained by the following formula is preferably 20% or less. More preferably, it is 17% or less. If the CV value exceeds 20%, fibers with a diameter of 20 ⁇ m or more that cause troubles due to infusibilization increase, which is not preferable from the viewpoint of productivity.
- S i is the fiber diameter dispersity
- 10,000 i is the average fiber diameter.
- S i is obtained by the following equation (2).
- D is the fiber diameter of each of the n fibers
- ten thousand is the average value of the n fiber diameters
- n is the number of fibers.
- the thermal conductivity of the carbon fiber composite sheet can be measured by a known method.
- the probe method, the hot disk method, and the laser flash method are preferable, and the probe method is particularly simple. I like it.
- the thermal conductivity of carbon fiber itself is about several hundred WZ (mK) .
- WZ WZ
- the carbon fiber composite sheet is 2 WZ (m-K) or more. Realized.
- the thermal conductivity is preferably 3 W / (mK) or more, more preferably 5 W / (mK) or more, more preferably 7 WZ (mK) or more, particularly preferably 10 WZ. (m-K) or more.
- it can be expected to be about 60 OW / (m-K), which is the thermal conductivity of a single carbon fiber.
- the proportion of the carbon fiber aggregates based on the carbon fiber composite sheet is in the range of 15 to 50% in terms of volume fraction (25 to 70% in terms of weight fraction). Is preferred. When it is within this range, when it is within this range, the resulting carbon fiber composite sheet can have both high thermal conductivity and mechanical properties.
- thermosetting silicone gel component a thermosetting epoxy resin component, and a thermosetting silicone resin component can be used as the thermosetting resin component that is cured after being combined with the carbon fiber aggregate. These can be arbitrarily selected according to the final use of the obtained carbon fiber composite sheet.
- thermosetting silicone gel component when tackiness is imparted to the carbon fiber composite sheet, a thermosetting silicone gel component is used, and when it is not desired to generate a volatile component from the carbon fiber composite sheet when heated, it is thermosetting.
- examples of using a thermosetting silicone resin component can be given, but the present invention is not limited to these, and appropriately according to the purpose. You can choose.
- thermosetting silicone gel component preferably has a viscosity of 0.01 to 2000 Pa.s at least in the range of 0 to 30 ° C, and curing occurs at 70 to 200 ° C. A component that completes curing in about 1 to 120 minutes is preferably used.
- thermosetting silicone gel component has an addition reaction type and a condensation reaction type.
- the addition reaction type can be preferably used.
- a thermosetting silicone gel component specifically, SE series SE 1 886, SE 1885, etc., which are thermosetting silicone gel components manufactured by Toray Dowco Ichining Co., Ltd., should be used. Can do. These have low viscosity and good workability.
- thermosetting epoxy resin component is not particularly limited, but a liquid liquid having a viscosity of 0.01 to 200 Pa ⁇ s at least in the range of 0 to 30 ° C. can be preferably used.
- a thermosetting epoxy resin component specifically, heat produced by Japan Epoxy Resin Co., Ltd. “J ER” 827, “j ER” 871, (formerly “Epicoat” 827, “Epicoat” 87 1), etc., which are curable epoxy resin components, can be used. These have low viscosity and good workability.
- the thermosetting epoxy resin component is cured using a curing agent.
- the curing agent is not particularly limited, but is modified aliphatic amine, modified aromatic amine, modified alicyclic amine, 3-methyl-1,2,3,6-tetrahydrophthalic anhydride, 4-methylol 1 , 2, 3, 6-tetrahydrophthalic anhydride, methylolene-3, 6-endomethylene-1, 2, 3, 6-tetrahydrophthalic anhydride, etc. can be used.
- “j ER Cure” FL 240 (formerly “Epicoat Cure” FL 240) manufactured by Japan Epoxy Resin Co., Ltd. can be used as a commercial product.
- the curing agent may be used in an amount of 10 to 50 parts by weight based on 100 parts by weight of the thermosetting epoxy resin component. Curing takes place at 70 to 200 ° C and takes about 1 to 180 minutes. Complete.
- thermosetting silicone resin component preferably has a viscosity of at least 0 to 30 ° C. and a viscosity of 0.01 to 10 Pa ′s. Hardening occurs at 70-200 ° C and ends in 1-180 minutes.
- thermosetting silicone resin component there are an addition reaction type and a condensation reaction type, but an addition reaction type in which the third component is hardly involved can be suitably used.
- SE series 821 etc. which is a thermosetting silicone component manufactured by Toray Dow Corning Co., Ltd. can be used. These have low viscosity and good workability.
- thermosetting resin component is a thermosetting silicone gel.
- the aspect which is a component is a component.
- the thermosetting resin component is a thermosetting silicone gel component
- the average fiber diameter of the carbon fibers is 1 to 20 m
- the thermal conductivity of the carbon fiber composite sheet is 3 WZ ( m ⁇ K) or more.
- the average fiber diameter is more preferably 3 to 15 ⁇ m, and still more preferably 5 to 12 ⁇ m.
- the average fiber length of the carbon fibers is preferably in the range of 0.01 to 1,000 mm.
- the average fiber length is more preferably 0.1 to 500 mm, and more preferably 3 to 300 mm.
- the hardness of the obtained carbon fiber composite sheet is measured by the penetration described in JISK6249.
- the penetration is preferably in the range of 30 to 90. Below 30, flexibility is lost and the ability to follow complex shapes is impaired. On the other hand, if it exceeds 90, it becomes extremely weak against piercing and may cause practical problems.
- thermosetting silicone gel preferably has a needle penetration of 90 or less after it is made into a carbon fiber composite sheet, and in particular, has a hardness of 90 or less after heat treatment at 200 ° C. for 4 hours. preferable.
- the 180 degree peel adhesive strength (tackiness) of carbon fiber composite sheets can be evaluated by 1 80 degree peel adhesive strength according to JISZ 0 2 37.
- the 180 degree peel adhesive strength is 0.0. 5 to 1.
- O ONZcm is preferable. If it is less than 5 N / cm, the carbon fiber composite sheet cannot have sufficient tackiness, and the contact between the heating element and the heat sink I cannot expect a result. On the other hand, if the tackiness is stronger than 1.0 ON / cm, the adhesiveness is too strong and the handling property is deteriorated.
- thermosetting resin component is a thermosetting epoxy resin component.
- thermosetting resin component is a thermosetting epoxy resin component
- the average fiber diameter of the carbon fiber is 5 to 20 ⁇ m
- the thermal conductivity of the carbon fiber composite sheet is 5 WZ (m -K)
- the average fiber diameter is more preferably 3 to 15 ⁇ , and still more preferably 5 to 12 ⁇ m.
- the average fiber length of the carbon fibers is preferably in the range of 0.01 to 100 Omm.
- the average fiber length is more preferably 0.1 to 500 mm, more preferably 3 to 300 mm.
- the obtained carbon fiber composite sheet has a mass reduction rate of 1 at 150 ° C. after 4 hours of heat treatment. % Or less is preferable. 1 When the mass reduction rate after heat treatment at 50 ° C. for 4 hours is 1% or less, since the volatile component is small by heating, it can be suitably used for electronic parts.
- thermosetting resin component is a thermosetting silicone resin component (1).
- the thermosetting resin component is a thermosetting silicone resin component, has a hardness of 70 or less on a Asker C hardness meter, and a carbon fiber aggregate when a carbon fiber composite sheet is used as a reference is
- the ratio of volume fraction is in the range of 20 to 50% (30 to 70% by weight fraction), and the thermal conductivity of the carbon fiber composite sheet is 3 W / (m ⁇ K) or more.
- the hardness of the first force C hardness tester is 70 or less, sufficient flexibility can be exhibited.
- both the thermal conductivity of the obtained carbon fiber composite sheet and the moldability during the production of the carbon fiber composite sheet are compatible. It can be made. More preferably, the volume fraction is 20 to 40% (weight fraction 30 to 60%). Although the thickness of the carbon fiber composite sheet can be freely set depending on the application, 0.2 to 1 O mm is preferable for improving the molding yield, and uniform molding without thickness unevenness can be easily performed. It is possible.
- the viscosity of the thermosetting silicone resin component before curing is preferably from 0.01 to 10 Pa ⁇ s. When it is within this range, the possibility of defects and the like can be reduced when the carbon fiber aggregate and the thermosetting silicone resin component are combined.
- thermosetting silicone resin component is preferably a component that is cured by being held at 100 ° C. for 1 hour. By using a component that cures by such treatment, the productivity of the carbon fiber composite sheet can be increased.
- thermosetting silicone resin component is preferably a component which comprises at least a main agent and a curing agent, and has a hardness of 70 or less on the Asker C hardness meter after being cured.
- the resin alone after thermosetting exceeds the Asker C hardness of 70, the carbon fiber composite sheet does not have an Asker C hardness of 70 or less. Therefore, it is preferable to use a component having an Asker C hardness of 70 or less in the resin unit after the heat effect.
- thermosetting resin component is a thermosetting silicone resin component. (2) for embodiments that are minutes.
- the thermosetting resin is a thermosetting silicone resin component
- the carbon fiber aggregate and the thermosetting silicone resin component are mixed by a uniaxial horizontal kneading device and a Z or paddle type vertical kneading device.
- the mixture is molded and the thermosetting silicone resin component is cured.
- the hardness of the ASKER C hardness tester is 70 or less, and the proportion of the carbon fiber aggregates based on the carbon fiber composite sheet is the volume fraction. It is preferably in the range of 15 to 30% by weight (25 to 50% by weight fraction).
- the Asker C hardness tester is 20 to 50.
- the proportion of the carbon fiber aggregates based on the carbon fiber composite sheet may be in the range of 15 to 30% in terms of volume fraction (25 to 50% in terms of weight fraction). Although it is preferable, when it is within this range, the resulting carbon fiber composite sheet has good thermal conductivity. Also, the viscosity of the mixture at the time of mixing does not become too high.
- the viscosity of the thermosetting silicone resin component before curing is from 0.001 to 10 Pa ⁇ s. When it is within this range, the possibility of defects and the like can be reduced when the carbon fiber aggregate and the thermosetting silicone resin component are combined. More preferably, it is 0.0 0 1 to 2 Pa ⁇ s.
- thermosetting silicone resin component is preferably a component that is cured by holding at 180 ° C. for 15 minutes. Such a thermosetting silicone resin component is preferred for producing a molded product because of its high curing speed. Les.
- thermosetting silicone resin component is preferably a component which comprises at least a main agent and a curing agent, and has a hardness of 70 or less on the Asker C hardness meter after being cured.
- Asker C hardness is 70 or less, flexibility can be imparted.
- the viscosity of the mixture obtained by mixing the carbon fiber aggregate and the thermosetting silicone resin component with the axial horizontal kneading device and / or the paddle type vertical kneading device is 30 ° C. Any of share rates 1 to 10 per second. In this case, it is preferably 1 0 0 0 0 Pa ⁇ s or less. In such a mixture, the fluidity is high, so that the moldability in extrusion molding, casting molding, press molding and the like is good. More preferably, the viscosity of the mixture is not more than 50 0 Pa ⁇ s at any one of 30 to 30 ° C share rate per second, and more preferably the viscosity of the mixture is 1 to 1 at 30 ° C share rate per second.
- thermosetting silicone resin component Any of 0 is 5 0 Pa • s or less. Viscosity all affects handling. In addition, since this viscosity does not become lower than the viscosity of the thermosetting silicone resin component, it goes without saying that the lower limit is the viscosity of the thermosetting silicone resin component.
- (A) to (D) are preferred embodiments and are not limited thereto.
- the carbon fiber composite sheet described above can be usefully used as a heat conductive molded body, a radio wave shielding molded body, a heat exchanger, and the like.
- the carbon fiber aggregate is impregnated with a thermosetting resin component, and then a press molding method or an injection molding method is used. Examples thereof include a method of molding by any one of an extrusion molding method and a casting molding method.
- a preferable embodiment for producing the carbon fiber composite sheet is as follows.
- an extruding step of extruding a mixture obtained by mixing a carbon fiber aggregate and a thermosetting silicone resin component with an axial horizontal kneading device and a Z or paddle type vertical kneading device onto a continuous carrier film Further, a film sticking process for sticking a continuous film, a compression process for passing the mixture sandwiched between the films between at least a pair of rollers having a certain clearance, and a heat treatment process for the compressed mixture are sequentially performed.
- An example of the manufacturing method is as follows.
- a mixture having a controlled viscosity composed of a carbon fiber aggregate and a thermosetting silicone resin component is used as a starting material. This is passed through an extrusion process in which it is extruded onto a carrier film using an extruder. In the extrusion process, the mixture may be discharged at a constant flow rate from a constant clearance called a lip, but a method of extruding by natural fall can also be adopted.
- the mixture discharged from the discharge port is received by a carrier film and transported. Since the mixture flows out from the discharge port continuously, the carrier film that receives this must also be continuous. This film can be continuously supplied from an under-printer.
- a cover film is also applied to the air layer side of the extruded mixture. This is a film sticking process.
- the mixture sandwiched between the carrier films is formed to have a constant thickness by passing between at least a pair of rollers having a determined clearance. This process is a compression process.
- a carbon fiber composite sheet can be obtained by passing the compressed mixture through a heat treatment step.
- the thermosetting silicone resin component can be cured by applying an energy equivalent to a heat treatment at 180 ° C. for 15 minutes.
- a hot air dryer or the like can be used, and any known heat treatment method can be employed within the scope of the object of the present invention.
- the carbon fiber composite sheet that has undergone the curing process can also be continuously wound into a wound mouth shape in a winding process or the like.
- the carrier film a polymer film having a melting point of 180 ° C. or higher is preferably used, and a polyethylene terephthalate film, a polyethylene naphthalate film, or the like can be preferably used.
- a polyethylene terephthalate film, a polyethylene naphthalate film, or the like can be preferably used.
- the carbon fiber composite sheet obtained in this way may be subjected to processing such as pressure-sensitive adhesive treatment on the surface, and can be used as a heat conductive molded body by sticking to an adhesive material or directly on a heating element. .
- the molded body should be used as a heat-dissipating member, heat-conducting member or constituent material for effectively dissipating heat generated by electronic components such as semiconductor elements, power supplies, and light sources in electronic devices. Can do. In recent years, these parts have a complicated shape and can be followed.
- the carbon fiber composite sheet of the present invention can be easily cut with a scissors or the like. More specifically, it is processed into an arbitrary shape that can form a shaping die and used between a heat-generating member such as a semiconductor element and a heat-dissipating member such as a heat sink, or a heat sink or semiconductor package component.
- Heat sink heat spreader It can be used after being molded into die pads, printed wiring boards, cooling fan parts, heat pipes, housings, etc. It can be used three-dimensionally as well as planarly. In the case of a heat pipe, it becomes possible to make it flexible.
- the carbon fiber aggregate before mixing with the thermosetting silicone resin is a mat in which the carbon fibers are three-dimensionally entangled inside the aggregate, and the carbon fiber aggregate in the mixture is in the form of the mat. It is preferable to carry out the mixing operation until it is no longer. By doing so, a homogeneous mixture can be obtained, so that the moldability can be improved.
- the fact that it is no longer in the form of a mat means that it does not retain the form as a fiber aggregate, and the carbon fiber is dispersed in the thermosetting silicone resin component.
- the appearance is usually a laver boiled. Even in such a state, the carbon fiber is not cut further, so that the thermal conductivity is sufficiently maintained.
- a method in which the carbon fiber aggregate is first unwound and mixed with the thermoplastic silicone resin component is preferable.
- the method of unwinding can be exemplified by cutting with a cutter, crushing with compressed air, or cutting by hand. It can also be achieved by adding a predetermined amount of the carbon fiber aggregate to the liquid silicone resin component and stirring with the above-mentioned kneading apparatus. In order to implement these efficiently, it is desirable to combine crushing operation and kneading operation.
- the average fiber diameter of carbon fibers was determined by measuring the diameter of 60 baked fibers using a scale under an optical microscope and taking the average value.
- the average fiber length of carbon fibers was determined by measuring the fiber length of 60 baked fibers with a length measuring instrument.
- the crystallite size of the carbon fiber was determined by the Gakushin method by measuring the reflection from the (1 10) plane appearing in X-ray diffraction.
- the 180 degree peel adhesive strength of the carbon fiber composite sheet was determined by the 180 degree peel adhesive force described in JI S Z 0 237.
- the carbon fiber composite sheet was left in a hot air dryer at 150 ° C. for 4 hours to determine the mass change before and after the heat treatment. From this, the mass reduction rate was determined.
- the hardness of the carbon fiber composite sheet and the silicone resin component was determined by a Asker C hardness tester.
- a pitch made of a condensed polycyclic hydrocarbon compound was used as a main raw material.
- the optical anisotropy ratio was 100% and the softening point was 283 ° C.
- heated air is squeezed out of the slit at a linear velocity of 550 Om per minute, and the melt pitch is pulled to produce a pitch short fiber with an average fiber diameter of 14.5 ⁇ .
- the spun fiber is collected on the bed and made into a mat. Further, a fiber assembly made of pitch-based short fibers having a basis weight of 3 20 g / m 2 was obtained by cross wrapping.
- the fiber assembly was infusibilized by raising the temperature from 1700 ° C. to 285 ° C. at an average temperature rise rate of 6 ° C. Zmin.
- the infusibilized pitch-based short fiber aggregate was fired at 2300 ° C.
- the average fiber diameter of the carbon fiber aggregate after firing was 9.8 ⁇ , and the ratio of the fiber diameter dispersion to the average fiber diameter was 12%.
- the average fiber length was 5 Omm.
- the crystallite size derived from the growth direction of the hexagonal mesh plane was 17 nm.
- the carbon fiber aggregate was obtained as a pine in which carbon fibers were entangled three-dimensionally inside the carbon fiber aggregate.
- the density of the carbon fiber was 2. O gZc m 3 .
- the thermal conductivity of the molded carbon fiber composite sheet was measured and found to be 6.4 W / (m ⁇ K).
- the penetration of the carbon fiber composite sheet was 45. 20 ° (:, after 4 hours of heat treatment, the penetration of the carbon fiber composite sheet was 40.
- the 180 ° peel adhesion of the carbon fiber composite sheet was 0.25 N / cm.
- a carbon fiber assembly was produced in the same manner as in Example 1. Then Toleda Using UC Jung SE 1 8 8 5, prepare two pieces of the gel component coated with a weight of 2 10 gZm 2 using a bar coater on a metal coated with a release material, and mold a carbon fiber aggregate The body volume ratio was set to 25% (weight ratio: 40%), and the thickness was set to 5 mm, and the weight was set to 270 g / m 2 in a die with a weight of 30 Omm. Then, press molding was performed at 150 ° C using a vacuum press manufactured by Kitagawa Seiki Co., Ltd.
- the thermal conductivity of the molded carbon fiber composite sheet was measured and found to be 6.4 W / (m ⁇ K).
- the penetration of the carbon fiber composite sheet was 75.
- the penetration of the carbon fiber composite sheet after heat treatment at 200 ° C for 4 hours was 70.
- the carbon fiber composite sheet had an 80-degree peel-off adhesive strength of 0.20 N / cm Example 3
- a pitch made of a condensed polycyclic hydrocarbon compound was used as a main raw material.
- the optical anisotropy ratio was 100%, and the softening point was 28 3 ° C.
- heated air was pumped from the slit at a linear velocity of 5 50 Om per minute, pulling the melt pitch, and an average fiber diameter of 14.5 ⁇ . Fibers were made.
- the spun fibers were collected on a belt to make a mat, and further, a fiber assembly made of pitch-based short fibers having a basis weight of 320 gZm 2 by cross-wrapping.
- This fiber assembly was infusibilized by raising the temperature from 1 ° C. to 285 ° C. in air at an average temperature increase rate of 6 ° C./min.
- the infusible fiber assembly was fired at 300 ° C.
- the average fiber diameter of the carbon fiber aggregate after firing was 9.6 m, and the ratio of the fiber diameter dispersion to the average fiber diameter was 10%.
- the average fiber length was 3 Om m.
- the crystallite size derived from the hexagonal network growth direction is 31 nm. there were.
- the carbon fiber aggregate was obtained as a mat in which carbon fibers were entangled three-dimensionally inside the carbon fiber aggregate.
- the density of the carbon fiber was 2.2 gZ cm 3 .
- SE 1886 manufactured by Toray Dow Corning Co. was used as the thermosetting silicone gel component.
- the heat conductivity of the molded carbon fiber composite sheet was measured and found to be 9.6 W / (m.K).
- the penetration of the carbon fiber composite sheet was 40.
- the penetration of the carbon fiber composite sheet after heat treatment at 200 ° C for 4 hours was 35.
- the carbon fiber composite sheet had an 80 degree peel-off adhesive strength of 0.3 ON / cm o
- a carbon fiber assembly was produced in the same manner as in Example 3. Next, SE 1885 manufactured by Toray Dow Coung Co., Ltd. was used as a thermosetting silicone gel component. Prepare two sheets of gel coated with a weight of 175 g / m 2 using a bar coater on the metal coated with the release agent, and the carbon fiber aggregate has a volume ratio of 25% (weight ratio). It was set to a die with a weight of 280 g / m 2 and a weight of 300 mm, so that the thickness was 0.5 mm. Then, press molding was performed at 150 ° C. with a vacuum press manufactured by Kitagawa Seiki Co., Ltd.
- a carbon fiber composite sheet was produced in the same manner as in Example 1 except that the firing temperature was 1300 ° C.
- the volume ratio of the carbon fiber aggregate to the compact was 25% (weight ratio of 38), and the crystallite size derived from the growth direction of the hexagonal network surface was 3 nm.
- the density of the carbon fiber was 1.8 gZcm 3 .
- the thermal conductivity of the molded carbon fiber composite sheet was measured and found to be 1.4 W / (m-K).
- the penetration of the carbon fiber composite sheet was 45.
- the penetration of the carbon fiber composite sheet after heat treatment at 200 ° C for 4 hours was 40.
- the carbon fiber composite sheet had an adhesive strength of 0.25 NZcm when peeled at 180 degrees.
- the thermal conductivity was not a sufficient value.
- Example 2 The carbon fiber composite sheet produced in Example 1 was loaded with 20 g of a weight heated to 70 ° C. and heated for 150 seconds to bring the temperature of the carbon fiber composite sheet to about 70 ° C. After that, when the weight was removed and the heat was dissipated, it reached 20 ° C after 60 seconds. It was found that the heat dissipation effect was high. Comparative Example 2
- Example 1 a thermosetting silicone was used without using a carbon fiber aggregate.
- a sheet was prepared using only the gel component, and 20 g of weight heated to 70 ° C was placed on it and heated for 50 seconds to bring the temperature of the silicone gel to about 70 ° C. After that, when the weight was removed and the heat was dissipated, the temperature reached 50 ° C after 60 seconds, and the heat dissipation was worse than that of the carbon fiber composite sheet.
- Example 6
- Example 1 a sheet was prepared using only the thermosetting silicone gel component without using the carbon fiber assembly, and the near-field blocking performance of radio waves of 1 to 3 GHz was measured. 6 dB, which is smaller than Example 7
- a pitch made of a condensed polycyclic hydrocarbon compound was used as a main raw material.
- the optical anisotropy ratio was 100%, and the softening point was 283 ° C.
- heated air is drawn from the slit at a linear velocity of 5 500 m / min, and the melt pitch is pulled to pull the short fiber with an average fiber diameter of 14.5 111 Was made.
- the spun fibers were collected on a belt to form a mat, and then a fiber assembly made of pitch-based short fibers having a basis weight of 320 gZm 2 by cross wrapping.
- This fiber assembly was infusibilized by raising the temperature from 170 ° C. to 285 ° C. in air at an average temperature rising rate of 6 ° C. Zmin. 2300 ° C of infusible fiber assembly Baked in.
- the average fiber diameter of the carbon fiber aggregate after firing was 9.8 ⁇ , and the ratio of the fiber diameter dispersion to the average fiber diameter was 12%.
- the average fiber length was 5 Om m.
- the crystallite size derived from the growth direction of the hexagonal mesh plane was 17 nm.
- the carbon fiber aggregate was obtained as a mat in which carbon fibers were entangled three-dimensionally inside the carbon fiber aggregate.
- the density of the carbon fiber was 2.0 g / cm 3 .
- J ER 871 (formerly “Epicoat” 871 manufactured by Japan Epoxy Resin Co., Ltd.) 100% by weight
- j ER Cure” FL 240 (formerly “Epicure” FL 240) manufactured by Japan Epoxy Resin Co., Ltd. )
- volume ratio becomes 25% (40% in volume ratio), so as to have a thickness of a 0. 5 mm, with the weight per unit area of 270 gZm 2, was set in a mold of internal dimensions 30 Omm.
- press molding was performed at 120 ° C using a vacuum press manufactured by Kitagawa Seiki Co., Ltd.
- the thermal conductivity of the molded carbon fiber composite sheet was measured and found to be 6.2 W / (m ⁇ K). 1
- the mass loss rate after heat treatment at 50 ° C. for 4 hours was 0.3%.
- a pitch made of a condensed polycyclic hydrocarbon compound was used as a main raw material.
- the optical anisotropy ratio was 100%, and the softening point was 283 ° C.
- heated air is ejected from the slit at a linear velocity of 550 Om per minute, and the melt pitch is pulled to produce a pitch short fiber with an average fiber diameter of 14.5 / m. did.
- the spun fibers are collected on a belt and used as a mat.
- a fiber assembly made of pitch-based short fibers having a basis weight of 320 g / m 2 was obtained by cross-wrapping.
- the fiber assembly was infusibilized by raising the temperature from 170 ° C. to 285 ° C. in air at an average temperature rising rate of 6 ° C. Zmin.
- the infusible fiber assembly was fired at 3000 ° C.
- the average fiber diameter of the carbon fiber aggregate after firing was 9.
- the ratio of the fiber diameter dispersion to the average fiber diameter was 10%.
- the average fiber length was 30 mm.
- the crystallite size derived from the growth direction of the hexagonal mesh plane was 3 l nm.
- the carbon fiber aggregate was obtained as a mat in which carbon fibers were entangled three-dimensionally inside the carbon fiber aggregate.
- the density of the carbon fiber was 2.2 gZcm 3 .
- Example 7 except that the firing temperature was 1 300 ° C.
- a carbon fiber composite sheet was prepared in the same manner as in 1.
- the volume ratio of the carbon fiber aggregate to the compact was 25% (weight ratio of 38), and the crystallite size derived from the growth of the hexagonal mesh surface was 3 nm.
- the density of the carbon fiber was 1.8 gZcm 3 .
- the thermal conductivity of the molded carbon fiber composite sheet was measured and found to be 1.4 WZ (m ⁇ K).
- the mass reduction rate of the carbon fiber composite sheet after heat treatment at 150 ° C. for 4 hours was 0.3%.
- the thermal conductivity was not sufficient. Comparative Example 5
- a carbon fiber assembly was prepared in the same manner as in Example 7. Then, instead of the thermosetting epoxy resin component, using SE 1 740 (E Redauko made-learning Co., Ltd.), the barcode one coater to a metal coated with a release material, of the resin 2 1 0 gZm 2 270 gZm 2 Prepare two sheets coated on the basis weight, and make the carbon fiber aggregate so that the volume ratio of the compact is 25% (40% by weight) and the thickness is 0.5 mm. The weight was set in a 300 mm inner die. Then, press molding was performed at 120 ° C using a vacuum press machine manufactured by Kitagawa Seiki Co., Ltd.
- the heat conductivity of the molded carbon fiber composite sheet was measured and found to be 5.6 W / (m ⁇ K).
- the mass reduction rate after heat treatment at 1550 ° C. for 4 hours was 2.1%. Mass reduction rate was large.
- Example 7 The carbon fiber composite sheet produced in Example 7 was placed on a 20 g weight heated to 70 ° C and heated for 150 seconds to bring the temperature of the carbon fiber composite sheet to about 70 ° C. . After that, when the weight was removed and the heat was dissipated, it reached 20 ° C after 60 seconds. It was found that the heat dissipation effect was high. Comparative Example 6
- Example 7 a sheet was prepared using only the thermosetting epoxy resin component without using the carbon fiber assembly, and a 20 g weight heated to 70 ° C. was placed on it and heated for 150 seconds. The temperature of the epoxy resin was about 70 ° C. After that, when the weight was removed and the heat was dissipated, the temperature reached 50 ° C after 60 seconds, and the heat dissipation was worse than that of the carbon fiber composite sheet.
- Example 1 0
- Example 7 a sheet was produced using only the thermosetting epoxy resin component without using the carbon fiber aggregate, and the near-field shielding performance of radio waves of 1 to 3 GHz was measured.
- Example 10 6 dB smaller than 0.
- a pitch made of a condensed polycyclic hydrocarbon compound was used as a main raw material.
- the optical anisotropy ratio was 100% and the softening point was 2 86 ° C.
- the heated fiber is ejected from the slit attached to the outlet hole at a linear velocity of 5500 m / min. . 5 ⁇ pitch short fibers were produced.
- the spun fiber The material was collected on a belt to make a mat, and then a fiber aggregate made of pitch-based short fibers having a basis weight of 290 g / m 2 by cross wrapping.
- the fiber assembly was infusibilized by raising the temperature from 170 ° C. to 285 ° C. at an average temperature rising rate of 6 ° C./min.
- the infusible fiber assembly was fired at 2300 ° C.
- the average fiber diameter of the carbon fiber aggregate after firing was 8.2 / m, and the ratio of the fiber diameter dispersion to the average fiber diameter (CV value) was 14%.
- the average fiber length was 1 1 Omm.
- the crystallite size derived from the growth direction of the hexagonal mesh plane was 20 nm.
- the carbon fiber aggregate was obtained as a mat in which the carbon fibers were entangled three-dimensionally inside the carbon fiber aggregate.
- the density of the carbon fiber was 2. O gZcm 3 .
- thermosetting silicone resin component SE 1 740 manufactured by Toray Dowco Ichining Co., Ltd. consisting of a main agent and a curing agent was used.
- the viscosity of the thermosetting silicone resin component was 1. l Pa ⁇ s in the range of at least 0-30 ° C.
- the hardness of the thermosetting silicone resin component alone was 11 according to the Asker C hardness tester.
- the carbon fiber composite sheet was taken out after holding at 100 ° C. for 1 hour, and the hardness was 45 measured by a Asker C hardness tester. When the thermal conductivity was measured, it was 6.5 W / (m ⁇ K).
- thermosetting silicone resin component A carbon fiber assembly was produced in the same manner as in Example 11. Next, S 1885 manufactured by Toray Dow Corning Co., Ltd., which consists of a main agent and a curing agent, was used as the thermosetting silicone resin component.
- the viscosity of the thermosetting silicone resin component was 1. l Pa ⁇ s in the range of at least 0-30 ° C.
- the Asker C hardness of the thermosetting silicone resin component alone was 5.
- thermosetting silicone resin component coated with a weight of 180 g / m 2 using a doctor knife on a stainless steel plate coated with a release agent.
- a doctor knife on a stainless steel plate coated with a release agent was set to a mold with a weight of 278 g / m 2 at a weight of 30 Omm, so that the thickness became 30% (46% by weight) and the thickness became 0.5 mm.
- press molding was performed at 150 ° C using a vacuum press manufactured by Kitagawa Seiki Co., Ltd.
- the carbon fiber composite sheet was taken out after holding at 100 ° C. for 1 hour, and the hardness was 45 measured by a Asker C hardness tester. The measured thermal conductivity was 7.1 W / (m ⁇ K).
- thermosetting silicone resin component SE 1 886 manufactured by Toray Dow Corning Co., Ltd. consisting of a main agent and a curing agent was used.
- the viscosity of the resin component was 0.5 Pa ⁇ s in the range of at least 0 to 30 ° C.
- the hardness of the thermosetting silicone resin component alone was 3 in terms of C force.
- a carbon fiber assembly was produced in the same manner as in Example 11.
- thermosetting silicone resin component SE 1 8 2 1 made by Toray Dow Corning Co., Ltd. consisting of a main agent and a curing agent was used.
- the viscosity of the resin component was 0.9 Pa ⁇ s in the range of 0 to 30 ° C.
- the hardness of the thermosetting 4-silicone resin component alone was 40 on the Asker C hardness tester.
- the carbon fiber composite sheet was taken out after holding at 100 ° C. for 1 hour, and the hardness was measured with a Asker C hardness tester to be 63. The measured thermal conductivity was 6.1 W / (m.K).
- Example 1 5 The carbon fiber composite sheet was taken out after holding at 100 ° C. for 1 hour, and the hardness was measured with a Asker C hardness tester to be 63. The measured thermal conductivity was 6.1 W / (m.K).
- a pitch made of a condensed polycyclic hydrocarbon compound was used as a main raw material. Optically anisotropic The sex ratio was 100% and the softening point was 283 ° C. Using a cap with a hole diameter of 0.2 mm ⁇ , heated air is ejected from the slit at a linear velocity of 5500 m / min, pulling the melt pitch to produce pitch-based short fibers with an average fiber diameter of 14.5 ⁇ . Produced. The spun fibers were collected on a belt to make a mat, and further, a fiber assembly made of pitch-based short fibers having a basis weight of 320 gZm 2 by cross-wrapping.
- the fiber assembly was infusibilized by raising the temperature from 170 ° C. to 285 ° C. in air at an average temperature rising rate of 6 ° C. Zmin.
- the infusible fiber assembly was fired at 3000 ° C.
- the average fiber diameter of the carbon fiber aggregate after firing was 9.6 m, and the ratio of the fiber diameter dispersion to the average fiber diameter (CV value) was 11%.
- the average fiber length was 6 Omm.
- the crystallite size derived from the growth direction of the hexagonal mesh plane was 46 nm.
- the carbon fiber aggregate was obtained as a pine in which carbon fibers were entangled three-dimensionally inside the carbon fiber aggregate.
- the density of the carbon fiber was 2.2 gZcm 3 .
- thermosetting silicone resin component S E 1 740 manufactured by Toray Dow Corning Co., Ltd. consisting of a main agent and a curing agent was used.
- the viscosity of the resin component was 1.1 Pa ⁇ s.
- the hardness of the thermosetting silicone resin component alone was 11 according to the Asker C hardness tester.
- thermosetting silicone resin component coated with a weight of 180 g / m 2 using a doctor knife on a metal plate coated with a release agent, and the carbon fiber aggregate volume ratio of the molded body was set to a die with a weight of 278 g / m 2 and a weight of 300 mm, so that the thickness would be 30% (49% by weight) and the thickness would be 0.5 mm.
- press molding was performed at 150 ° C using a vacuum press machine manufactured by Kitagawa Seiki Co., Ltd.
- Example 15 SE 6 74 6 AZB composed of a thermosetting silicone resin component composed of a main agent and a curing agent and having a viscosity of at least 2 0 0 Pa ⁇ s in the range of 0 to 30 ° C was used.
- a carbon fiber composite sheet was prepared in the same manner except for the above.
- the hardness of the produced carbon fiber composite sheet was measured with a Asker C hardness tester to be 64.
- the thermal conductivity was 6.2 WZ (m ⁇ K).
- the thermosetting silicone resin component application with a doctor knife the occurrence of uneven thickness was in an acceptable range except for applications where strict uniformity of thickness was not required.
- Example 15 The carbon fiber composite sheet prepared in 5 was placed at a temperature of 70 ° C., and 20 g of a weight was placed on the carbon fiber composite sheet and held for 1550 seconds. The temperature was about 70 ° C. After that, when the weight was removed and the heat was released, the temperature of the part that was in contact with the weight after 50 seconds was 30 ° C. It was found that the heat dissipation effect was high. Comparative Example 8
- Example 15 without using a carbon fiber aggregate, a sheet in which a thermosetting silicone resin component is formed into a sheet is prepared, and 20 g of a weight heated to 70 ° C. is placed on the sheet 1 Holding for 50 seconds, the resin temperature at the weight contact part was adjusted to about 70 ° C. After that, after removing the weight and dissipating heat, 60 seconds later The heat dissipation effect was lower than that of the carbon composite sheet obtained by the operation of Example 16.
- Example 18
- Example 15 In Example 15 and without using a carbon fiber aggregate, a sheet in which a thermosetting silicone resin component was formed into a sheet was prepared, and the near-field blocking performance of radio waves of 1 to 3 GHz was measured. B, which did not have sufficient near-field blocking performance for 1 to 3 GHz radio waves.
- Example 1 9 In Example 15 and without using a carbon fiber aggregate, a sheet in which a thermosetting silicone resin component was formed into a sheet was prepared, and the near-field blocking performance of radio waves of 1 to 3 GHz was measured. B, which did not have sufficient near-field blocking performance for 1 to 3 GHz radio waves.
- Example 1 9 Example 1 9
- a pitch made of a condensed polycyclic hydrocarbon compound was used as a main raw material.
- the optical anisotropy ratio was 100% and the softening point was 283 ° C.
- Using a hole cap with a diameter of 0.2 ⁇ draw heated air from the slit at a linear velocity of 5500 m / min, pulling the melt pitch to produce pitch-type short fibers with an average fiber diameter of 11.5 / m Produced.
- the spun fibers were collected on a belt to make a mat, and further, a fiber assembly made of pitch-based short fibers having a basis weight of 310 g / m 2 by cross-rubbing.
- the fiber assembly was infusibilized by raising the temperature from 170 ° C. to 295 ° C. in air at an average rate of temperature increase of 6 ° CZ.
- the infusible fiber assembly was fired at 2300 ° C.
- the average fiber diameter of the carbon fibers constituting the carbon fiber aggregate after firing is 8.3 ⁇ , and the ratio of fiber diameter dispersion to average fiber diameter (CV) is 14%. there were.
- the average fiber length was 8 Omm.
- the crystallite size derived from the growth direction of the hexagonal mesh plane was 15 nm.
- the carbon fiber aggregate was obtained as a pine in which the carbon fibers were entangled three-dimensionally inside the carbon fiber aggregate.
- the density of the carbon fiber was 2. O gZcm 3 .
- thermosetting silicone resin component S E 1 740 manufactured by Toray Dow Corning Co., Ltd. consisting of a main agent and a curing agent was used.
- the viscosity of the resin component was 1. l Pa ⁇ s in the range of at least 0-30 ° C.
- the hardness of the silicone resin component alone after heat treatment at 180 ° C for 15 minutes was 11 according to the Asker C hardness tester.
- the carbon fiber aggregate and the main component of the thermosetting silicone resin component are agitated with a paddle type vertical kneader, and further the curing agent of the thermosetting silicone resin component is added, and the volume fraction is 30% (by weight fraction).
- a mixture in which 46%) of carbon fiber aggregates were dispersed until the form of the mat disappeared was prepared.
- the viscosity of the mixture was 56 Pa ⁇ s at 30 ° C and a shear rate of 1.7 per second.
- a 75 ⁇ m polyethylene terephthalate film was used as the carrier vinylome, and the mixture was extruded onto a carrier film with a coater.
- 75 m of polyethylene terephthalate phenolic was laminated as a cover vinylome.
- it was passed through between rollers having a clearance of 1 mm, and further passed through a single nozzle having a clearance of 0.5 mm to form a compression process. Thereafter, it was cured by a heat treatment at 180 ° C. for 15 minutes with a hot air dryer.
- Example 20 A carbon fiber assembly was produced in the same manner as in Example 19.
- thermosetting silicone resin component S E 1 885 manufactured by Toray Dow Corning Co., Ltd. consisting of a main agent and a curing agent was used.
- the viscosity of the resin component was l P a ⁇ s in the range of at least 0-30 ° C.
- the hardness of the silicone resin component alone at 180 ° C and 15 minutes after curing was 8 with a Asker C hardness meter.
- Example 21 Disperse and mix the carbon fiber aggregate and the main component of the thermosetting silicone resin component with a paddle type vertical kneader until the mat shape disappears, and add the curing agent of the thermosetting silicone resin component. To obtain a mixture.
- the viscosity of the mixture was 74 Pa ⁇ s at 30 ° C and a shear rate of 1.7 per second.
- the carbon fiber composite sheet was produced with the manufacturing method similar to Example 19.
- the carbon fiber composite sheet thus prepared had an Asker C hardness of 40.
- the thermal conductivity was 3.8 W / (m-K).
- a carbon fiber assembly was produced in the same manner as in Example 19.
- thermosetting silicone resin component SE 1 886 manufactured by Toray Dow Co. Jung Co., Ltd. consisting of a main agent and a curing agent was used.
- the viscosity of the resin component was at least 0.5 Pa ⁇ s in the range of 0 to 30 ° C.
- thermosetting silicone resin component Disperse and mix the carbon fiber aggregate and the main component of the thermosetting silicone resin component with a paddle type vertical kneader until the mat form disappears, and then mix the curing agent of the thermosetting silicone resin component to obtain a mixture. .
- the viscosity of the mixture was 59 ° Pa ⁇ s at 30 ° C and a shear rate of 1.7 per second.
- a carbon fiber composite sheet was produced by the same production method as in Example 19.
- the carbon fiber composite sheet thus produced had an Asker C hardness of 39.
- the thermal conductivity was 3.3 W / (m-K).
- a carbon fiber assembly was produced in the same manner as in Example 19.
- thermosetting silicone resin component SE 1 82 1 manufactured by Toray Dow Corning Co., Ltd. consisting of a main agent and a curing agent was used.
- the viscosity of the resin component was at least 0.9 Pa ⁇ s in the range of 0 to 30 ° C.
- the hardness of the silicone resin component alone when cured at 180 ° C. for 15 minutes was 40 on the Asker C hardness scale.
- thermosetting silicone resin component The carbon fiber aggregate and the main component of the thermosetting silicone resin component are dispersed and mixed with a paddle type vertical kneader until the form of the mat disappears, and further the curing agent of the thermosetting silicone resin component is mixed to obtain a mixture. .
- the viscosity of the mixture was 106 Pa ⁇ s at 30 ° C and a shear rate of 1.7 per second.
- a carbon fiber composite sheet was produced by the same production method as in Example 19.
- the Asker C hardness of the carbon fiber composite sheet thus prepared was 58.
- the thermal conductivity was 3. OW / (m ⁇ K).
- a pitch made of a condensed polycyclic hydrocarbon compound was used as a main raw material.
- the optical anisotropy ratio was 100% and the softening point was 283 ° C.
- heated air was ejected from the slit at a linear velocity of 5500 m / min, and the melt pitch was pulled to produce pitch-based short fibers with an average fiber diameter of 14.5 ⁇ . .
- the spun fibers are collected on a belt and used as a mat. Further, a fiber assembly made of pitch short fibers having a basis weight of 3 30 g Zm 2 was obtained by cross-wrapping.
- This fiber assembly was infusibilized by raising the temperature from 1700 ° C. to 29.5 ° C. at an average temperature raising rate of 6 ° C./min.
- the infusible fiber assembly was fired at 300 ° C.
- the average fiber diameter of the carbon fibers constituting the carbon fiber aggregate after firing was 9.6 ⁇ , and the ratio of the fiber diameter dispersion to the average fiber diameter (CV) was 11%.
- the average fiber length was 6 Omm.
- the crystallite size derived from the growth direction of the hexagonal mesh plane was 46 nm.
- the carbon fiber aggregate was obtained as a pine in which the carbon fibers were entangled three-dimensionally inside the carbon fiber aggregate.
- the density of the carbon fiber was 2.2 gZcm 3 .
- thermosetting silicone resin component S 1 7 40 0 manufactured by Toray Dow Corning Co., Ltd., which comprises a main agent and a curing agent, was used.
- the viscosity of the resin component was 1. l Pa ⁇ s in the range of 0 to 30 ° C. Further, the hardness of the silicone resin component alone was 1800 ° C., and after curing for 15 minutes, the Asker C hardness was 1 1.
- thermosetting silicone resin component curing agent is added to give a volume fraction of 30% (4% by weight). 9%) of carbon fiber aggregates were dispersed until the form of the mat disappeared.
- the viscosity of the mixture was 45 ° Pa ⁇ s at 30 ° C. and a shear rate of 1.7 per second.
- a 75 ⁇ polyethylene terephthalate film was used as the carrier vinylome, and the mixture was extruded onto a carrier film with a coater. Next, 75 ⁇ m of polyethylene terephthalate phenol was bonded as a force perinolem. Next, the clearance is passed between 1 mm rollers, and the clearance is further passed between 0.5 mm rollers and the compression process. did. Thereafter, as a heat treatment, it was treated with a hot air type dryer at 180 ° C. for 15 minutes.
- the Asker C hardness of the carbon fiber composite sheet thus prepared was 36.
- the thermal conductivity was 5.4 WZmK. Comparative Example 1 0
- Example 1 paddle type vertical kneading of carbon fiber aggregate with 10% volume fraction (18% by weight fraction) and thermosetting silicone resin component with 90% volume fraction.
- the mixture was stirred with an apparatus.
- the viscosity of the mixture was 20 Pa ⁇ s at 30 ° C. shear rate 1.7 per second.
- the Asker C hardness of the carbon fiber composite sheet produced by the same production method as in Example 1 was 27.
- the thermal conductivity was 1.2 WZmK. Comparative Example 1 1
- Example 19 the paddle type vertical kneading of carbon fiber aggregates with 45% volume fraction (62% by weight fraction) and thermosetting silicone resin component with 55% volume fraction The same operation was performed except that the mixture was prepared by stirring with the apparatus. The mixture had a viscosity of 30 ° C. and a shear rate of 1-7 per second, and was 300 ° Pa ⁇ s. Thus, a flat carbon fiber composite sheet could not be produced due to poor extrudability.
- Example 19 The carbon fiber composite sheet produced in 9 was loaded with 20 g of weight heated to 70 ° C and held for 15 seconds, and the temperature of the weight contact portion of the carbon fiber composite sheet was adjusted. The temperature was about 70 ° C. After that, if you remove the weight and let it radiate heat At about 50 seconds, the temperature of the part that was in contact with the weight was 37 ° C. It was found that the heat dissipation effect was high. Comparative Example 1 2
- Example 19 without using a carbon fiber aggregate, a sheet in which a thermosetting silicone resin component was formed into a sheet was prepared, and a 20 g weight heated to 70 ° C was placed on the sheet for 150 seconds. The resin temperature at the holding and weight contact area was about 70 ° C. Thereafter, when the weight was removed and the heat was radiated, it reached 55 ° C after 60 seconds, and the heat radiated was worse than that of the carbon composite sheet used in Example 19.
- Example 25
- Example 19 a sheet in which a thermosetting silicone resin component alone was formed into a sheet without using a carbon fiber aggregate, and the near-field blocking performance of radio waves of 1 to 3 GHz was measured. Therefore, it did not have sufficient near-field cutoff performance of 1 to 3 GHz radio waves.
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
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Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US12/298,745 US7947362B2 (en) | 2006-04-27 | 2007-04-26 | Carbon fiber composite sheet |
EP07742861A EP2025704A4 (en) | 2006-04-27 | 2007-04-26 | CARBON COMPOSITE FABRIC |
JP2008513332A JPWO2007126133A1 (ja) | 2006-04-27 | 2007-04-26 | 炭素繊維複合シート |
Applications Claiming Priority (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2006-123379 | 2006-04-27 | ||
JP2006123379 | 2006-04-27 | ||
JP2006199482 | 2006-07-21 | ||
JP2006-199482 | 2006-07-21 | ||
JP2006-247998 | 2006-09-13 | ||
JP2006247998 | 2006-09-13 | ||
JP2006-264197 | 2006-09-28 | ||
JP2006264197 | 2006-09-28 |
Publications (1)
Publication Number | Publication Date |
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WO2007126133A1 true WO2007126133A1 (ja) | 2007-11-08 |
Family
ID=38655648
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/JP2007/059426 WO2007126133A1 (ja) | 2006-04-27 | 2007-04-26 | 炭素繊維複合シート |
Country Status (6)
Country | Link |
---|---|
US (1) | US7947362B2 (ja) |
EP (1) | EP2025704A4 (ja) |
JP (1) | JPWO2007126133A1 (ja) |
KR (1) | KR20080114838A (ja) |
TW (1) | TW200804087A (ja) |
WO (1) | WO2007126133A1 (ja) |
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US20120025111A1 (en) * | 2009-03-27 | 2012-02-02 | Richard Bryant | Electromagnetic field absorbing composition |
WO2013073546A1 (ja) * | 2011-11-16 | 2013-05-23 | 東レ株式会社 | 繊維強化複合材料および繊維強化複合材料の製造方法 |
JP2013104033A (ja) * | 2011-11-16 | 2013-05-30 | Toray Ind Inc | 繊維強化複合材料および繊維強化複合材料の製造方法。 |
JP2013245253A (ja) * | 2012-05-24 | 2013-12-09 | Toray Ind Inc | 繊維強化複合材料およびその製造方法 |
JP2016143815A (ja) * | 2015-02-04 | 2016-08-08 | 住友ベークライト株式会社 | パワーモジュール用放熱樹脂シート、その製造方法、パワーモジュールおよびその製造方法 |
JP2018161766A (ja) * | 2017-03-24 | 2018-10-18 | 学校法人 龍谷大学 | 炭素繊維三次元構造体及びその製造方法 |
WO2019107247A1 (ja) * | 2017-11-29 | 2019-06-06 | 帝人株式会社 | 複合材料、成形体の製造方法、及び複合材料の製造方法 |
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WO2020093161A1 (en) * | 2018-11-07 | 2020-05-14 | Regen-Composites International Corp. | Material created from polymer and other mass which is entirely, partially or substantially composed of reclaimed mixed material |
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- 2007-04-26 JP JP2008513332A patent/JPWO2007126133A1/ja not_active Withdrawn
- 2007-04-26 KR KR1020087028100A patent/KR20080114838A/ko not_active Application Discontinuation
- 2007-04-26 US US12/298,745 patent/US7947362B2/en not_active Expired - Fee Related
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JP2009209507A (ja) * | 2008-02-06 | 2009-09-17 | Teijin Ltd | ピッチ系炭素繊維フェルト及び炭素繊維含有断熱材 |
US20120025111A1 (en) * | 2009-03-27 | 2012-02-02 | Richard Bryant | Electromagnetic field absorbing composition |
US9806426B2 (en) * | 2009-03-27 | 2017-10-31 | Qinetiq Limited | Electromagnetic field absorbing composition |
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JP2013104033A (ja) * | 2011-11-16 | 2013-05-30 | Toray Ind Inc | 繊維強化複合材料および繊維強化複合材料の製造方法。 |
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JP2016143815A (ja) * | 2015-02-04 | 2016-08-08 | 住友ベークライト株式会社 | パワーモジュール用放熱樹脂シート、その製造方法、パワーモジュールおよびその製造方法 |
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JPWO2019107247A1 (ja) * | 2017-11-29 | 2020-11-19 | 帝人株式会社 | 複合材料、成形体の製造方法、及び複合材料の製造方法 |
JPWO2019107248A1 (ja) * | 2017-11-29 | 2020-11-19 | 帝人株式会社 | 複合材料及びその製造方法 |
US11795279B2 (en) | 2017-11-29 | 2023-10-24 | Teijin Limited | Composite material, production method for molded object, and production method for composite material |
JP2020176182A (ja) * | 2019-04-16 | 2020-10-29 | 信越化学工業株式会社 | 自己粘着性を有する異方性熱伝導性シート |
CN110981487A (zh) * | 2019-11-22 | 2020-04-10 | 航天特种材料及工艺技术研究所 | 一种陶瓷基改性碳纤维隔热材料的制备方法 |
Also Published As
Publication number | Publication date |
---|---|
TW200804087A (en) | 2008-01-16 |
KR20080114838A (ko) | 2008-12-31 |
US20090233092A1 (en) | 2009-09-17 |
EP2025704A4 (en) | 2010-11-24 |
JPWO2007126133A1 (ja) | 2009-09-17 |
EP2025704A1 (en) | 2009-02-18 |
US7947362B2 (en) | 2011-05-24 |
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