CN101646814B - Pitch-derived carbon fiber, process for producing the same, and molded object - Google Patents
Pitch-derived carbon fiber, process for producing the same, and molded object Download PDFInfo
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- CN101646814B CN101646814B CN200880007053.9A CN200880007053A CN101646814B CN 101646814 B CN101646814 B CN 101646814B CN 200880007053 A CN200880007053 A CN 200880007053A CN 101646814 B CN101646814 B CN 101646814B
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Abstract
The purpose of the invention is to provide carbon fibers which have high thermal conductivity, readily form a network in a matrix, and are suitable for use in a radiating member; and a molded object containing the fibers. The pitch-derived carbon fibers are characterized by being produced from mesophase pitch as a raw material and having an average fiber diameter (AD) of 5-20 [mu]m, a coefficient of fiber diameter variation in percentage based on the average fiber diameter (AD), CV<AD> value, of 5-15, a number-average fiber length (NAL) of 25-500 [mu]m, a volume-average fiber length (VAL) of 55-750 [mu]m, and a value obtained by dividing the volume-average fiber length (VAL) by the number-average fiber length (NAL) of 1.02-1.50. Also provided is a process for producing the fibers.
Description
Technical field
The present invention relates to pitch class (ピ Star チ system) carbon fiber and preparation method thereof, this pitch-based carbon fiber has specific fibre diameter and fibre length, and its distribution is arranged in specific scope.The invention still further relates to the good formed body of heat conductivity that has used pitch-based carbon fiber.
Background technology
High performance carbon fiber can be divided into polyacrylonitrile (PAN) as the PAN based carbon fiber of raw material with the pitch-based carbon fiber of pitch class as raw material.And, utilize the intensity of carbon fiber, the characteristic that elastic modelling quantity is obviously high than common synthetic high polymer, it is widely used in aviation, universe purposes; Building, building purposes; Physical culture, leisure purposes etc.
Compare with common synthetic high polymer, the carbon fiber pyroconductivity is high, and thermal diffusivity is good.Carbon fiber is because the mobile realization high thermoconductivity of phonon (phonon).Phonon transmits in the material of lattice prosperity.But the not talkative lattice of commercially available PAN based carbon fiber is very flourishing, and its pyroconductivity considers from the viewpoint of heat management that usually less than 200W/ (mK) it is certain suitable to be difficult to say so.Relative therewith, pitch-based carbon fiber is high because of graphitization, and lattice is very flourishing, compares with the PAN based carbon fiber, realizes high thermoconductivity easily.
In recent years, along with miniaturization, thin typeization and the lightweight of electronic equipments such as the densification of exothermicity electronic unit, portable personal computer, the requirement of the low thermal resistanceization of use therein thermal component uprises gradually, requires further to improve heat dissipation characteristics.As thermal component, but example: the heat conductivity sheet that comprises the solidfied material of having filled the heat conductivity filler; Be included in the heat conductivity isolator (spacer) of having filled the solidfied material heat conductivity filler, that have flexibility in the spawn; In aqueous matrix (matrix), filled the mobile heat conductivity paste that has of heat conductivity filler; With solvent dilution heat conductivity paste, further improved mobile heat conductivity coating; In the curable material, filled the heat conductivity binding agent of heat conductivity filler; Utilized the inversion of phases thermal component etc. of the phase change of resin.
For improving the pyroconductivity of these thermal components, can in matrix, fill a large amount of heat conducting materials.As heat conducting material, (patent documentations 1) such as metal oxides such as known aluminium oxide, boron nitride, aluminium nitride, magnesia, zinc oxide, carborundum, quartz, aluminium hydroxide, metal nitride, metal carbides, metal hydroxides.Yet the heat conducting material proportion of class of metal materials is high, causes the weight of thermal component to increase.In addition, under the situation of using pulverous heat conducting material, owing to be difficult to form network (network), so be difficult to obtain high heat conductivity.Therefore, in improving heat conductivity, need a large amount of heat conducting materials that use, the result is that the weight of thermal component increases, cost increases, and is necessarily to be to use material easily hardly.
Therefore, for effectively utilizing the high conductance of heat conducting material, preferably heat conducting material forms network in the state between suitable matrix.As the shape of easy formation network, well-known fibrous material (patent documentation 2).
Fibrous material has carbon fiber.Carbon fiber is used in carbon fiber reinforced plastic etc. (patent documentation 3) because of its rigidity, heat resistance.In addition, application (patent documentation 4) in electrode for secondary battery etc. has been proposed.
Also proposed in heat conducting material, to use carbon fiber.For example in patent documentation 5, proposed, used average fiber length more than 30 μ m and the fin of the celion of less than 300 μ m.In addition, in patent documentation 6, proposed, used and to contain the heat conducting device of composition that length is the carbon fiber of 10～150 μ m.In patent documentation 7, proposed, contained the semiconductor device of the graphitized carbon fibre that is coated with kicker magnet.Yet, in patent documentation 5～7, be not used in and improve the dispersed Research of carbon fiber in matrix, exist the network that improves carbon fiber and form ability and the leeway of improving heat conductivity.
(patent documentation 1) TOHKEMY 2005-72220 communique
(patent documentation 2) Japan special table 2002-535469 communique
(patent documentation 3) japanese kokai publication hei 7-90725 communique
(patent documentation 4) japanese kokai publication hei 7-85862 communique
(patent documentation 5) TOHKEMY 2000-192337 communique
(patent documentation 6) japanese kokai publication hei 11-279406 communique
(patent documentation 7) TOHKEMY 2002-146672 communique
Summary of the invention
The object of the present invention is to provide the excellent carbon fiber of heat conductivity that is suitable for thermal component.In addition, the object of the present invention is to provide high, the easy carbon fiber that in matrix, forms network of heat conductivity.In addition, the object of the present invention is to provide the preparation method of this carbon fiber.In addition, the object of the present invention is to provide the high formed body of network, heat conductivity that forms carbon fiber on matrix middle-high density ground.
The carbon fiber that hope is used in thermal component forms network easily in matrix, have high heat conductivity simultaneously.The inventor has studied heat conductivity and network forms the excellent carbon fiber of ability.The result finds that in the thermal component that contains carbon fiber and matrix, as carbon fiber, if use the big pitch-based carbon fiber of crystal size, then the heat conductivity of thermal component improves.Also find in addition, if make the fibre length in the thermal component be in specific scope, suppress fibre length distribution, make it even as far as possible, then form the network of carbon fiber easily, heat conductivity improves.Find also that in addition if make the fibre diameter in the thermal component be in specific scope, and make the distribution of fibre diameter be in specific scope, then heat conductivity further improves.The present invention is based on these opinions and accomplish.
Namely, the present invention is a pitch-based carbon fibers, wherein the mesophase pitch as the raw material, the average fiber diameter (AD) of 5 ~ 20μm, the fiber diameter distribution to average fiber diameter (AD) the percentage (mean Fiber diameter (AD ) Outward ni su ru Full Fiber diameter distribution percentages) (CV
AD value) from 5 to 15, the number average fiber length (number-average? fiber? lenth) (NAL) is 25 ~ 500μm, the volume average fiber length (volume-average? fiber? lenth) (VAL) of 55 ~ 750μm, the volume average fiber length (VAL) divided by number average fiber length (NAL) value of 1.02 to 1.50.
In addition, the present invention includes the formed body that uses above-mentioned carbon fiber.
In addition; The present invention is the preparation method of pitch-based carbon fiber; It is characterized in that, the mesophase pitch of fusion is carried out spinning, again through not melting (not melting), fire, pulverizing and prepare pitch-based carbon fiber with meltblown; In the method, the viscosity of the mesophase pitch of fusion is 5～25PaS during spinning.
In addition; The present invention includes the method for the heat conductivity that improves the thermal component that contains carbon fiber and matrix; The method is characterized in that; Use following pitch-based carbon fiber as this carbon fiber: be raw material with mesophase pitch, fiber diameter (AD) is 5～20 μ m, and the fibre diameter decentralized photo is for the percentage (CV of fiber diameter (AD)
ADValue) be 5～15, number average fiber length (NAL) is 25～500 μ m, and volume averaging fibre length (VAL) is 55～750 μ m, is 1.02～1.50 with volume averaging fibre length (VAL) divided by the value of number average fiber length (NAL).
The specific embodiment
Then, embodiment of the present invention is described.
(pitch-based carbon fiber)
(average fiber length: NAL, VAL)
The number average fiber length (NAL) of carbon fiber of the present invention is 25～500 μ m, and volume averaging fibre length (VAL) is 55～750 μ m, is 1.02～1.50 with volume averaging fibre length (VAL) divided by the value (VAL/NAL) of number average fiber length (NAL).
Number average fiber length (NAL) is preferably 50～500 μ m, and more preferably 100～500 μ m further are preferably 100～400 μ m.
Volume averaging fibre length (VAL) is preferably 60～750 μ m, more preferably 100～600 μ m.
VAL/NAL is preferably 1.1～1.4, and more preferably 1.15～1.35.
If number average fiber length (NAL) less than 55 μ m, then can not fully form network between the carbon fiber in the matrix less than 25 μ m or volume averaging fibre length (VAL), can not bring into play high pyroconductivity.On the other hand, if number average fiber length (NAL) surpasses 500 μ m or volume averaging fibre length (VAL) surpasses 750 μ m, then the friendship network of fiber (friendship network) obviously increases, and viscosity becomes very big with mixed with resin the time, handles the difficulty that becomes.
Be meant the range of the fiber length distribution of carbon fiber divided by the value (VAL/NAL) of number average fiber length (NAL) with volume averaging fibre length (VAL).Under this was worth less than 1.02 situation, fibre length was almost completely identical, is practically impossible.In addition, under greater than 1.50 situation, mean that fiber length distribution is very wide, comprise very short or very long carbon fiber, cause pyroconductivity to descend or the viscosity rising.
Average fiber length can be controlled through pulverization conditions.That is, the rotating speed of the cutting machine in the time of can passing through to regulate with pulverizing such as cutting machines, the revolution of ball mill, the air velocity of airslide disintegrating mill, the collision frequency of crushing machine, the time of staying in the reducing mechanism, control average fiber length.In addition, can regulate removing the fibre length carbon fiber of carbon fiber after pulverizing short or that fibre length is long through the classification operation such as sieving.
(on sieve residual ratio)
Hope pitch-based carbon fiber of the present invention be 100～500 μ m in number average fiber length (NAL), when with aperture (order is opened I) being the sieve classification of sieve aperture (mesh) of 53 μ m, residual ratio is 30～60% on sieve; When with the aperture being the sieve classification of sieve aperture of 100 μ m, residual ratio is 10～29% on sieve.Be residual carbon fiber on the sieve of sieve aperture of 53 μ m in the aperture, be suitable for forming matrix, conduction is worked effectively to heat.In addition, residual carbon fiber on the sieve of the sieve aperture of 100 μ m, bulk density is high, therefore in matrix, hands over network and forms the space.Through in this space, being placed in short carbon fiber residual under the sieve aperture of 53 μ m, thereby make the occupied state of the carbon fiber in the matrix become good.Though this condition is able to suitably to satisfy, with the sieve classification of the sieve aperture of 53 μ m the time, residual ratio is 30～60% on sieve, and when in the use aperture being the sieve classification of sieve aperture of 100 μ m, residual ratio is 10～29% on sieve.Can be controlled at ratio residual on the sieve through control pulverization conditions and classification condition.
Be after pulverizing, to remove fibre length pitch-based carbon fiber filler short or fibre length length as concrete control method with sieve, sieve shape thing (mesh).In addition; The revolution of the intensity of pulverizing through control, the cutter of for example cutting machine, the revolution of ball mill, the air velocity of airslide disintegrating mill, the collision frequency of crushing machine, the time of staying in the reducing mechanism etc.; Distribution that can controlling fiber length; Through controlling and making up, can more critically control the ratio on the sieve with the control of sieve, sieve shape thing (mesh).
(fiber diameter: AD)
The fiber diameter of carbon fiber (AD) is 5～20 μ m.Under the situation of less than 5 μ m, with matrix composite the time, it is many that the radical of filler becomes, and therefore, the viscosity of the mixture of matrix/filler uprises, and difficulty is shaped.If surpass 20 μ m, then with matrix composite the time, the radical of filler tails off, and therefore, just is not easy contact between filler, when becoming composite, is not easy to bring into play effective heat conduction.Fiber diameter (AD) is preferably 5～15 μ m, more preferably 7～13 μ m.
The fibre diameter decentralized photo is for the percentage (CV of fiber diameter (AD)
ADValue) be 5～15.
CV
ADValue can be tried to achieve by following formula:
CV
AD＝S/AD (1)
Here, S is the fibre diameter decentralization, and AD is a fiber diameter.
In addition, S can be tried to achieve by following formula (2):
Here, D is the fibre diameter of each fiber, and n is the number of measuring.
CV
ADBe worth more for a short time, mean that process stability is high, product inhomogeneous little.CV
ADValue was less than 5 o'clock, and fibre diameter reaches unanimity, and therefore was difficult between filler, insert the little filler of fibre diameter, with matrix composite the time, was difficult to add in a large number, and the result is difficult to obtain high performance composite.Otherwise, at CV
ADValue is greater than under 15 the situation, and with matrix composite the time, it is irregular to be easy to generate viscosity, the dispersed reduction.As a result, become inhomogeneous, can not produce the uniform thermal conducting rate in the dispersion of the filler of composite inner.CV
ADValue can be when regulating spinning the viscosity of mesophase pitch of fusion realize, specifically, can be through when utilizing meltblown to carry out spinning, the molten asphalt during with spinning is adjusted into 5～25PaS and realizes.
(crystallite size)
Carbon fiber of the present invention, the crystallite size that preferably derives from the direction of growth of hexagonal wire side is more than the 5nm.The crystallite size that derives from the direction of growth of hexagonal wire side can be tried to achieve through known method, and the diffracted ray of (110) face of carbon crystallization that can be through utilizing the X-ray diffraction method gained is tried to achieve.Crystallite size is why important to be because the heat conduction is mainly undertaken by phonon, and crystallization produces phonon.Crystallite size more preferably more than the 20nm, further is preferably more than the 30nm.The upper limit of crystallite size is about 100nm.
(real density)
The real density of carbon fiber is preferably 1.5～2.3g/cc, and more preferably 1.8～2.3g/cc further is preferably 2.1～2.3g/cc.In the time of in this scope, degree of graphitization is very high, can give full play to hot conductivity, and simultaneously, also the characteristic with the carbon fiber of gained is corresponding to be used for graphited cost of energy.
(pyroconductivity)
Carbon fiber fiber axis to pyroconductivity be preferably more than the 300W/mK, more preferably 600～1,100W/mK.Under the situation more than the 300W/mK, can obtain sufficient heat conductivity being mixed with under the situation of formed body with matrix.
(preparation method of pitch-based carbon fiber)
Pitch-based carbon fiber of the present invention can make as follows: with meltblown the mesophase pitch of fusion is carried out spinning, again through not melting, fire, pulverize, as required and classification prepares.Preferably after pulverizing, carry out graphitization processing.
(raw material)
As the raw material of pitch-based carbon fiber of the present invention, for example can enumerate fused polycycle hydrocarbon compounds such as naphthalene, phenanthrene; Condensed heterocyclic compouds such as petroleum-type pitch, coal class pitch etc.Wherein, fused polycycle hydrocarbon compounds such as preferred naphthalene, phenanthrene.Preferred especially optical anisotropy pitch, i.e. mesophase pitch.They can use a kind of separately, also can two or more appropriate combination be used, but use mesophase pitch that the heat conductivity of carbon fiber is improved separately, so preferred especially.
The softening point of material asphalt can use Mettler softening point method (メ ト ラ one method) to try to achieve, preferably more than 250 ℃ below 350 ℃.If softening point is lower than 250 ℃, then when not melting, produce fusion adhesion or big thermal contraction between the fiber.In addition, if softening point is higher than 350 ℃, the temperature that is suitable for spinning uprises, and thermal decomposition takes place pitch easily, and it is difficult that spinning becomes.
(spinning)
Material asphalt can be through discharging (spuing) and with the melt spinning of its cooling and fibration from nozzle after fusion.Do not have special restriction as spinning process, particularly can enumerate: the common spin processes that will batch from the pitch that nozzle (mouthful gold) is discharged with up-coiler; Adopt hot blast as the meltblown of spraying (atomizing) source; Utilize centrifugal spinning that centrifugal force batches pitch etc., but, preferably use meltblown from reasons such as productivity height.
Material asphalt preferably behind melt spinning, through not melting, fire, pulverizing, carries out graphitization at last.Below, be example with the meltblown, each operation is described.
In the present invention; Shape to as the spinning-nozzle of the pitch fibers of pitch-based carbon fiber raw material does not have special restriction, and the preferred spinning-nozzle that uses is: seal wire angle α is 10～90 °, the length L of outlet and the nozzle of ratio L/D in 6～20 scope of diameter D.Nozzle temperature during spinning gets final product so long as can keep the temperature of stable spinning state.For making the inhomogeneous little of fibre diameter, that is, make CV
ADBe in the scope of regulation, the viscosity of the molten asphalt during spinning is preferably 5～25PaS, more preferably 6～22PaS.According to the composition of material asphalt, be the content of effumability composition, and make the temperature dependency of viscosity of molten asphalt different, but specifically,, then can realize this viscosity mostly if the temperature of molten asphalt is adjusted into the temperature higher 40～60 ℃ than softening point.When spinning condition was in this scope, it was arrangement (assortment) to a certain degree that the shear load in the material asphalt can make aromatic rings.In the time of outside spinning condition is in this scope, for example in viscosity too small the seal wire angle is too small or the L/D condition that shear load is stronger when excessive etc. under, aromatic rings is exceedingly arranged, when graphitization, carbon fiber damages easily.Otherwise under or the condition that shear load such as the seal wire angle is excessive or L/D is too small is littler excessive in viscosity, aromatic rings is less arranged, and therefore, does not also more improve degree of graphitization even carry out graphitization processing, can not obtain high heat conductivity.
For pitch fibers, make short fiber by near the gas that refinement point (refinement point), sprays the linear velocity of the per minute 100～10000m that is heated to 100～350 ℃ from the nozzle bore wire vent.The temperature of gas is high approximately, then the time till the bitumen solidification elongated, the stretching action of performance longer time has the tendency that obtains thinner fiber.The preferred gas that sprays the temperature close with the melt temperature of material asphalt.Equally, the linear velocity of jet body big more, then the stronger stretching action of performance has the tendency that obtains thinner fiber.But if the linear velocity of gas is too high, then pitch fibers can fracture, after the loss stated on the wire guipure (gold net ベ Le ト) become big.Melt viscosity and the difference of preferred linear velocity during according to spinning, particularly, when melt viscosity was 100PaS, linear velocity was preferably per minute 3,000～7,000m.The gas that is sprayed can use air, nitrogen and argon gas, but considers from the cost performance aspect, preferred air.
Pitch fibers is caught to combine on the woven wire band, forms continuous felted (マ Star ト shape), and then becomes the three-dimensional random felt through cross lapping (cross lap).
The three-dimensional random felt is meant that except cross lapping, pitch fibers is handed over the felt of network also three-dimensionally.This friendship network is to realize to the tube that is called as chimney (chimney) the wire guipure from nozzle.Because the fiber of wire is handed over network three-dimensionally, so usually only show characteristic also reflection to some extent in solid of fiber of the behavior of one dimension.
(not melting)
To contain the three-dimensional random felt of the pitch fibers that as above obtains, not melt with known method.Do not melt and be to use air or ozone, nitrogen dioxide, nitrogen, oxygen, iodine, bromine are made an addition in the air and the gas that forms, under 200～350 ℃, carry out.Consider security and convenience, preferably in air, implement.
(firing)
In addition, will pass through infusible pitch fibers in a vacuum or in inert gases such as nitrogen, argon gas, krypton gas,, fire under 500 ℃ 600～1.Fire and many in the cheap nitrogen of normal pressure and cost, implement.
(pulverizing)
Can be through after not melting or after firing, pulverized fiber obtains pitch-based carbon fiber.Pulverizing can be carried out with known method.Specifically, can use cutting machine, ball mill, airslide disintegrating mill, crushing machine etc.
(classification)
For removing long carbon fiber of fibre length or short carbon fiber, preferably carbon fiber is carried out classification with sieve.The hole of removing the sieve of long carbon fiber is about 0.8～1mm, and the hole of removing the sieve of short carbon fiber is about 20 μ m.Repeat classification and can remove short or long carbon fiber, but only implement once also to have good effect.
This classification operation is still being carried out all as broad as longly after graphitization after the pulverizing, but pulverizer and grading plant can easily make up, and after pulverizing, carries out hierarchical processing and can carry out effectively, so preferably.
(graphitization)
As required, with the pitch-based carbon fiber classification of pulverizing, then preferably carry out graphitization.For improving the pyroconductivity as carbon fiber, graphitization temperature is preferably 2,000～3,500 ℃, more preferably 2,300～3,100 ℃, further is preferably 2,800～3,100 ℃.When graphitization,, then can cut off the physics from the outside, the effect of chemistry, so preferred as if handling in the crucible of putting into graphite property.As long as the crucible of graphite system can be put into above-mentioned carbon fiber with desired amount; The not restriction of its size and shape; But for prevent in graphitization processing or cooling in stove in oxidizing gas or steam reaction cause the carbon fiber damage, can suitably utilize the high crucible of air-tightness with cover.The form of the stove that usually uses according to graphitization changes the kind of inert gas.
(formed body)
Carbon fiber of the present invention and matrix composite can obtain formed bodies such as compound, tablet (sheet), grease (grease), binding agent.Therefore, the present invention comprises the formed body that uses this carbon fiber.
Formed body contains carbon fiber and matrix, and with respect to formed body 100 weight portions, the amount of carbon fiber is preferably 10～70 weight portions, more preferably 20～60 weight portions.As matrix, can use vistanex, mylar, polycarbonate resin, polyamide, polyimide resin, polyphenylene sulfide, polysulfone resin, polyethersulfone resin, polyether ketone resin, polyether-ether-ketone resin, epoxy resin, acrylic resin, phenolic resins (Off エ ノ one Le is a resin) and organic siliconresin etc.Formed body can be preferably as the thermal component of exothermicity electronic unit.
(improving the method for heat conductivity)
The present invention is the method that improves the heat conductivity of thermal component; This thermal component contains carbon fiber and matrix; It is characterized in that; Use following pitch-based carbon fiber as this carbon fiber: as raw material, fiber diameter (AD) is 5～20 μ m with mesophase pitch, and the fibre diameter decentralized photo is for the percentage (CV of fiber diameter (AD)
ADValue) be 5～15, number average fiber length (NAL) is 25～500 μ m, and volume averaging fibre length (VAL) is 55～750 μ m, is 1.02～1.50 with volume averaging fibre length (VAL) divided by the value of number average fiber length (NAL).
Carbon fiber and matrix are as stated.With respect to thermal component 100 weight portions, the amount of the carbon fiber in thermal component is preferably 10～70 weight portions, more preferably 20～60 weight portions.
Embodiment
Show embodiment below, but the present invention is not limited to this.Each value among the embodiment is tried to achieve according to following method.
(1) fiber diameter of carbon fiber (AD) is under light microscope, to use scale (scale) to measure the mean value through 60 carbon fiber gained firing.
(2) the average carbon fiber length of the number of carbon fiber (NAL) is to measure the mean value through 1,000 carbon fiber gained firing with device for measuring length.In addition, obtain actual measurement 1,000 fiber each fibre length square mean value, the square root of this mean value is volume averaging fibre length (VAL).
(3) crystallite size of carbon fiber is tried to achieve as follows: the reflection of (110) face that measures to occur in the comfortable X-ray diffraction, and try to achieve with the method (shake method) of shaking.
(4) density of carbon fiber is confirmed as follows: regulate bromoform (density is 2.90g/cc) and 1; 1,2, the mixing ratio of 2-ethylene tetrachloride (density is 1.59g/cc); Carbon fiber is put in the mixed liquor of having adjusted solution density, confirmed according to the sedimentation degree of carbon fiber.
(5) pyroconductivity of carbon fiber is tried to achieve as follows: use silver-colored paste to fix as the mode of 1cm with the two ends distance of graphitization pitch-based carbon fiber (this carbon fiber is the graphitization pitch-based carbon fiber of except that pulverizing operation, making with identical condition); Measure the resistance at 20 (20) two ends with measuring appliance; The radius of use carbon fiber calculates obtains resistivity, is calculated and is tried to achieve by the following relational expression (No. 3648865, referenced patent) of pyroconductivity and resistance:
K＝1272.4/ER-49.4
(K is the pyroconductivity W/ (mK) of carbon fiber, and ER is the resistivity μ Ω m of carbon fiber).
(6) pyroconductivity of carbon fiber/organic silicon composite, the QTM-500 that uses capital of a country electronics corporation to produce tries to achieve with sonde method.
(7) the pitch-based carbon fiber filler is tried to achieve in the last residual ratio of sieve (mesh) as follows: through the 100g carbon fiber is used the aperture is that 100 μ m, aperture are the sieve of 53 μ m; After sieving with concussion machine (タ Na カ テ Star Network produce R-1), measure gained carbon fiber quality and try to achieve.
Embodiment 1
With the pitch that contains the fused polycycle hydrocarbon compound as main material.The optical anisotropy ratio of this pitch is 100%, and softening point is 283 ℃.Use the lid of diameter as the hole of 0.2mm Φ, with per minute 5, ejection adds hot-air to the linear velocity of 500m from the slit, the drawing-off molten asphalt, and making average diameter is the pitch class staple fibre of 14.5 μ m.The resin temperature of this moment is 337 ℃, and melt viscosity is 8.0PaS.Spun fiber captured on being with, process felt, and then be 320g/m through cross lapping production unit area weight (order is paid)
2The three-dimensional random felt that forms by pitch class staple fibre.
This three-dimensional random felt is warmed up to 285 ℃ from 170 ℃ for 6 ℃/minute with average heating speed in air do not melt.To pulverize through infusible three-dimensional random felt with 800rpm with cutting machine (production of タ one Port industrial group),, gains fired under 3000 ℃ with the sieve classification of 1mm.
The fiber diameter of the carbon fiber after firing (AD) is 8.8 μ m, and the fibre diameter decentralized photo is 12% for the percentage (CV value) of fiber diameter (AD).
Number average fiber length (NAL) is 200 μ m; Volume averaging fibre length (VAL) is 240 μ m; Is 1.20 with volume averaging fibre length (VAL) divided by the value of number average fiber length (NAL) gained, and when using the aperture to be the sieve classification of sieve aperture of 53 μ m, residual ratio is 45% on sieve; When using the aperture to be the sieve classification of sieve aperture of 100 μ m, residual ratio is 24% on sieve.The crystallite size that derives from the direction of growth of hexagonal wire side is 70nm.Real density is 2.18g/cc, and pyroconductivity is 350W/mK.
Carbon fiber, 75 weight portion organic siliconresins (SE1740 that eastern レ ダ ウ シ リ コ one Application (strain) is produced) by with 25 weight portion gained mix, and under 130 ℃, carry out heat cure and handle, and obtain carbon fiber/organic silicon composite.Measure the pyroconductivity of the carbon fiber/organic silicon composite of made, the result is 6.3W/ (mK).
Embodiment 2
Except the revolution of the cutting machine among the embodiment 1 is changed into the 700rpm, make carbon fiber with identical method.
The fiber diameter of the carbon fiber after firing (AD) is 8.6 μ m, and the fibre diameter decentralized photo is 12% for the percentage (CV value) of fiber diameter (AD).Number average fiber length (NAL) is 300 μ m; Volume averaging fibre length (VAL) is 390 μ m; Is 1.30 with volume averaging fibre length (VAL) divided by the value of number average fiber length (NAL) gained; When using the aperture to be the sieve classification of sieve aperture of 53 μ m, residual ratio is 55% on sieve; When using the aperture to be the sieve classification of sieve aperture of 100 μ m, residual ratio is 29% on sieve.The crystallite size that derives from the direction of growth of hexagonal wire side is 70nm.Real density is 2.18g/cc, and pyroconductivity is 350W/mK.
Carbon fiber, 75 weight portion organic siliconresins (SE1740 that eastern レ ダ ウ シ リ コ one Application (strain) is produced) by with 25 weight portion gained mix, and under 130 ℃, carry out heat cure and handle, and obtain carbon fiber/organic silicon composite.Measure the pyroconductivity of the carbon fiber/organic silicon composite of made, the result is 6.6W/ (mK).
Comparative example 1
Except not carrying out the progressive operation of carrying out with sieve among the embodiment 1, make carbon fiber with identical method.
The fiber diameter of the carbon fiber after firing (AD) is 8.8 μ m, and the fibre diameter decentralized photo is 12% for the percentage (CV value) of fiber diameter (AD).Number average fiber length (NAL) is 250 μ m; Volume averaging fibre length (VAL) is 400 μ m; Is 1.60 with volume averaging fibre length (VAL) divided by the value of number average fiber length (NAL) gained; When using the aperture to be the sieve classification of sieve aperture of 53 μ m, residual ratio is 62% on sieve; When using the aperture to be the sieve classification of sieve aperture of 100 μ m, residual ratio is 33% on sieve.The crystallite size that derives from the direction of growth of hexagonal wire side is 70nm.Real density is 2.19g/cc, and pyroconductivity is 350W/mK.
Carbon fiber, 75 weight portion organic siliconresins (SE1740 that eastern レ ダ ウ シ リ コ one Application (strain) is produced) by with 25 weight portion gained mix, and under 130 ℃, carry out heat cure and handle, and obtain carbon fiber/organic silicon composite.Measure the pyroconductivity of the carbon fiber/organic silicon composite of made, the result is 3.3W/ (mK).
Comparative example 2
Except the revolution of the cutting machine among the embodiment 1 (cutter) is changed into the 1200rpm, make carbon fiber with identical method.
The fiber diameter of the carbon fiber after firing (AD) is 8.8 μ m, and the fibre diameter decentralized photo is 13% for the percentage (CV value) of fiber diameter (AD).Number average fiber length (NAL) is 40 μ m; Volume averaging fibre length (VAL) is 50 μ m; Is 1.13 with volume averaging fibre length (VAL) divided by the value of number average fiber length (NAL) gained; When using the aperture to be the sieve classification of sieve aperture of 53 μ m, residual ratio is 18% on sieve; When using the aperture to be the sieve classification of sieve aperture of 100 μ m, residual ratio is 3% on sieve.The crystallite size that derives from the direction of growth of hexagonal wire side is 70nm.Real density is 2.18g/cc, and pyroconductivity is 350W/mK.
Carbon fiber, 75 weight portion organic siliconresins (SE1740 that eastern レ ダ ウ シ リ コ one Application (strain) is produced) by with 25 weight portion gained mix, and under 130 ℃, carry out heat cure and handle, and obtain carbon fiber/organic silicon composite.Measure the pyroconductivity of the carbon fiber/organic silicon composite of made, the result is 1.4W/ (mK).
Comparative example 3
Except the revolution of the cutting machine among the embodiment 1 is changed into the 400rpm, carry out identical operations and make carbon fiber.
The fiber diameter of the carbon fiber after firing (AD) is 8.8 μ m, and the fibre diameter decentralized photo is 12% for the percentage (CV value) of fiber diameter (AD).Number average fiber length (NAL) is 600 μ m; Volume averaging fibre length (VAL) is 700 μ m; Is 1.17 with volume averaging fibre length (VAL) divided by the value of number average fiber length (NAL) gained; When using the aperture to be the sieve classification of sieve aperture of 53 μ m, residual ratio is 87% on sieve; When using the aperture to be the sieve classification of sieve aperture of 100 μ m, residual ratio is 59% on sieve.The crystallite size that derives from the direction of growth of hexagonal wire side is 70nm.Density is 2.18g/cc, and pyroconductivity is 350W/mK.
The carbon fiber of 25 weight portion gained, 75 weight portion organic siliconresins (SE1740 that eastern レ ダ ウ シ リ コ one Application (strain) is produced) are mixed, but the viscosity height can not make the tablet identical with embodiment 1.
Comparative example 4
Change into the 2.0PaS except the resin temperature among the embodiment 1 being changed into 345 ℃, melt viscosity, make carbon fiber with identical method.
The fiber diameter of the carbon fiber after firing (AD) is 8.4 μ m, and the fibre diameter decentralized photo is 19% for the percentage (CV value) of fiber diameter (AD).Number average fiber length (NAL) is 180 μ m; Volume averaging fibre length (VAL) is 240 μ m; Is 1.33 with volume averaging fibre length (VAL) divided by the value of number average fiber length (NAL) gained; When using the aperture to be the sieve classification of sieve aperture of 53 μ m, residual ratio is 49% on sieve; When using the aperture to be the sieve classification of sieve aperture of 100 μ m, residual ratio is 23% on sieve.The crystallite size that derives from the direction of growth of hexagonal wire side is 70nm.Real density is 2.18g/cc, and pyroconductivity is 350W/mK.
Carbon fiber, 75 weight portion organic siliconresins (SE1740 that eastern レ ダ ウ シ リ コ one Application (strain) is produced) by with 25 weight portion gained mix; And under 130 ℃, carry out heat cure and handle; Obtain carbon fiber/organic silicon composite, but the carbon fiber dispersion is inhomogeneous, obtains uneven formed body.
Comparative example 5
Except 3000 ℃ ablating work procedure among the embodiment 1 is changed into before pulverizing, carry out, make carbon fiber with identical method.
The fiber diameter of the carbon fiber after firing (AD) is 8.1 μ m, and the fibre diameter decentralized photo is 18% for the percentage (CV value) of fiber diameter (AD).Number average fiber length (NAL) is 210 μ m; Volume averaging fibre length (VAL) is 300 μ m; Is 1.43 with volume averaging fibre length (VAL) divided by the value of number average fiber length (NAL) gained; When using the aperture to be the sieve classification of sieve aperture of 53 μ m, residual ratio is 48% on sieve; When using the aperture to be the sieve classification of sieve aperture of 100 μ m, residual ratio is 26% on sieve.The crystallite size that derives from the direction of growth of hexagonal wire side is 70nm.Real density is 2.18g/cc, and pyroconductivity is 350W/mK.
Carbon fiber, 75 weight portion organic siliconresins (SE1740 that eastern レ ダ ウ シ リ コ one Application (strain) is produced) by with 25 weight portion gained mix; And under 130 ℃, carry out heat cure and handle; Obtain carbon fiber/organic silicon composite, but the viscosity height can not make the tablet identical with embodiment 1.
The result of embodiment 1～2, comparative example 1～5 is shown in table 1 and table 2.
Table 1
| Project | Unit | Embodiment 1 | Embodiment 2 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 |
| AD | μm | 8.8 | 8.6 | 8.8 | 8.8 | 8.8 | 8.4 | 8.1 |
| CV ADValue | ％ | 12 | 12 | 12 | 13 | 12 | 19 | 18 |
| NAL | μm | 200 | 300 | 250 | 40 | 600 | 180 | 210 |
| VAL | μm | 240 | 390 | 400 | 50 | 700 | 240 | 300 |
| VAL/NAL | - | 1.20 | 1.30 | 1.60 | 1.13 | 1.17 | 1.33 | 1.43 |
| Crystallite size | nm | 70 | 70 | 70 | 70 | 70 | 70 | 70 |
| Real density | g/cc | 2.18 | 2.18 | 2.19 | 2.18 | 2.18 | 2.18 | 2.18 |
| Pyroconductivity | W/m·K | 350 | 350 | 350 | 350 | 350 | 350 | 350 |
| Revolution | rpm | 800 | 700 | 800 | 1200 | 400 | 800 | 800 |
| Classification | - | Have | Have | Do not have | Have | Have | Have | Have |
| In the aperture is on the sieve of 53 μ m | ％ | 45 | 55 | 62 | 18 | 87 | 49 | 48 |
| In the aperture is on the sieve of 100 μ m | ％ | 24 | 29 | 33 | 3 | 59 | 23 | 26 |
AD: fiber diameter; NAL: number average fiber length; VAL: volume averaging fibre length
Table 2
| Project | Unit | Embodiment 1 | Embodiment 2 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 |
| Carbon fiber | Weight portion | ?25 | ?25 | ?25 | ?25 | ?25 | ?25 | ?25 |
| Organic siliconresin | Weight portion | ?75 | ?75 | ?75 | ?75 | ?75 | ?75 | ?75 |
| Pyroconductivity | W/(m· K) | ?6.3 | ?6.6 | ?3.3 | ?1.4 | ?- | ?- | ?- |
Embodiment 3
With the pitch that contains the fused polycycle hydrocarbon compound as main material.The optically anisotropic ratio of this pitch is 100%, and softening point is 283 ℃.Use the lid of diameter as the hole of 0.2mm Φ, with per minute 5, ejection adds hot-air to the linear velocity of 500m from the slit, the pitch of drawing-off fusion, and making average diameter is the pitch class staple fibre of 14.5 μ m.The resin temperature of this moment is 337 ℃, and melt viscosity is 8.0PaS.Spun fiber captured on being with, process felt, and then be 320g/m through cross lapping production unit area weight
2The three-dimensional random felt that forms by pitch class staple fibre.
This three-dimensional random felt is warmed up to 285 ℃ from 170 ℃ for 6 ℃/minute with average heating speed in air do not melt.To pulverize through infusible three-dimensional random felt with 800rpm with cutting machine (production of タ one Port industrial group), use the sieve classification of aperture, gains will be fired under 3000 ℃ as 1mm.The fiber diameter (AD) of the pitch-based carbon fiber filler after firing is 8.8 μ m, and the fibre diameter decentralized photo is 12 for the percentage (CV value) of fiber diameter (AD).Number average fiber length (NAL) is 200 μ m, and when using the aperture to be the sieve classification of sieve aperture of 53 μ m, residual ratio is 45% on sieve; When using the aperture to be the sieve classification of sieve aperture of 100 μ m, residual ratio is 24% on sieve.The crystallite size that derives from the direction of growth of hexagonal wire side is 70nm.Density is 2.18g/cc, and pyroconductivity is 350W/mK.
Carbon fiber, 75 weight portion organic siliconresins (SE1740 that eastern レ ダ ウ シ リ コ one Application (strain) is produced) by with 25 weight portion gained mix, and under 130 ℃, carry out heat cure and handle, and obtain carbon fiber/organic silicon composite.Measure the pyroconductivity of the carbon fiber/organic silicon composite of made, the result is 5.6W/ (mK).
Embodiment 4
Except the revolution of the cutting machine among the embodiment 1 is changed into the 900rpm, make the pitch-based carbon fiber filler with identical method.The fiber diameter (AD) of the pitch-based carbon fiber filler after firing is 8.8 μ m, and the fibre diameter decentralized photo is 12 for the percentage (CV value) of fiber diameter (AD).Number average fiber length (NAL) is 160 μ m, and when using the aperture to be the sieve classification of sieve aperture of 53 μ m, residual ratio is 35% on sieve; When using the aperture to be the sieve classification of sieve aperture of 100 μ m, residual ratio is 20% on sieve.The crystallite size that derives from the direction of growth of hexagonal wire side is 70nm.Density is 2.18g/cc, and pyroconductivity is 350W/mK.
Carbon fiber, 75 weight portion organic siliconresins (SE1740 that eastern レ ダ ウ シ リ コ one Application (strain) is produced) by with 25 weight portion gained mix, and under 130 ℃, carry out heat cure and handle, and obtain carbon fiber/organic silicon composite.Measure the pyroconductivity of the carbon fiber/organic silicon composite of made, the result is 4.8W/ (mK).
Embodiment 3 and 4 result are shown in table 3 and table 4.
Table 3
| Project | Unit | Embodiment 3 | Embodiment 4 |
| AD | μm | 8.8 | 8.8 |
| CV ADValue | ％ | 12 | 12 |
| NAL | μm | 200 | 160 |
| VAL | μm | 240 | 190 |
| VAL/NAL | - | 1.20 | 1.19 |
| Crystallite size | nm | 70 | 70 |
| Real density | g/cc | 2.18 | 2.18 |
| Pyroconductivity | W/m·K | 350 | 350 |
| Revolution | rpm | 800 | 900 |
| Classification | - | Have | Have |
| In the aperture is on the sieve of 53 μ m | ％ | 45 | 35 |
| In the aperture is on the sieve of 100 μ m | ％ | 24 | 20 |
AD: fiber diameter; NAL: number average fiber length; VAL: volume averaging fibre length
Table 4
| Project | Unit | Embodiment 3 | Embodiment 4 |
| Carbon fiber | Weight portion | 25 | 25 |
| Organic siliconresin | Weight portion | 75 | 75 |
| Pyroconductivity | W/(m·K) | 5.6 | 4.8 |
The effect of invention
Carbon fiber heat conductivity of the present invention is excellent, can be used for thermal component.Carbon fiber heat conductivity of the present invention is high, in matrix, forms network easily.
According to the preparation method of carbon fiber of the present invention, can this carbon fiber be processed the uneven carbon fiber of no fibre diameter.In addition, formed body of the present invention forms the carbon fibre web network on matrix middle-high density ground, and heat conductivity is high.
Industrial usability
Carbon fiber of the present invention can be used for the thermal component of exothermicity electronic unit etc.
Claims (10)
1. pitch-based carbon fiber is characterized in that, as raw material, fiber diameter AD is 5～20 μ m with mesophase pitch, and the fibre diameter decentralization is with respect to the percentage CV of fiber diameter AD
ADValue is 5～15, and number average fiber length NAL is 100～500 μ m, and volume averaging fibre length VAL is 55～750 μ m; Using volume averaging fibre length VAL is 1.02～1.50 divided by the value of number average fiber length NAL gained; When using the aperture to be the sieve classification of sieve aperture of 53 μ m, residual ratio is 30～60% on the sieve, when using the aperture to be the sieve classification of sieve aperture of 100 μ m; Residual ratio is 10～29% on the sieve
Said number average fiber length NAL is the mean value of 1,000 carbon fiber,
Said volume averaging fibre length VAL is, obtain 1,000 fiber each fibre length square mean value, the square root of this mean value is volume averaging fibre length VAL,
Said CV
ADValue is tried to achieve by following formula:
CV
AD＝S/AD (1)
Here, S is the fibre diameter decentralization, and AD is a fiber diameter,
S is tried to achieve by following formula (2):
Here, D is the fibre diameter of each fiber, and n is the number of measuring.
2. the described carbon fiber of claim 1 is characterized in that, the crystallite size that derives from the direction of growth of hexagonal wire side is more than the 5nm.
3. the described carbon fiber of claim 1 is characterized in that, real density is the scope of 1.5～2.3g/cc, fiber axis to pyroconductivity be more than the 300W/ (mK).
4. formed body, this formed body uses each described carbon fiber among claim 1-3.
5. formed body, this formed body contains each described carbon fiber and matrix among the claim 1-3, and with respect to formed body 100 weight portions, the content of carbon fiber is 10～70 weight portions.
6. the described formed body of claim 5; Wherein, matrix is to be selected from least a in vistanex, mylar, polycarbonate resin, polyamide, polyimide resin, polyphenylene sulfide, polysulfone resin, polyethersulfone resin, polyether ketone resin, polyether-ether-ketone resin, epoxy resin, acrylic resin, phenolic resins and the organic siliconresin.
7. the described formed body of claim 5, this formed body is a thermal component.
8. the preparation method of the described pitch-based carbon fiber of claim 1; It is through with meltblown the mesophase pitch of fusion being carried out spinning; And do not melt, fire, pulverize, then carry out the method that classification prepares pitch-based carbon fiber, it is characterized in that; The viscosity of the mesophase pitch of fusion is 5～25PaS during spinning, carries out classification with the sieve of 0.8～1mm.
9. the described preparation method of claim 8 is characterized in that, after pulverizing, under 2300～3100 ℃, carries out graphitization.
10. improve the method for the heat conductivity of the thermal component that contains carbon fiber and matrix, it is characterized in that,, use the pitch-based carbon fiber described in the claim 1 as this carbon fiber.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP055924/2007 | 2007-03-06 | ||
| JP055927/2007 | 2007-03-06 | ||
| JP2007055927 | 2007-03-06 | ||
| JP2007055924 | 2007-03-06 | ||
| PCT/JP2008/054245 WO2008108482A1 (en) | 2007-03-06 | 2008-03-04 | Pitch-derived carbon fiber, process for producing the same, and molded object |
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| CN101646814A CN101646814A (en) | 2010-02-10 |
| CN101646814B true CN101646814B (en) | 2012-03-28 |
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| JP2009013390A (en) * | 2007-06-04 | 2009-01-22 | Teijin Ltd | Thermally conductive sheet |
| JP2009108118A (en) * | 2007-10-26 | 2009-05-21 | Teijin Ltd | Pitch-based carbon short fiber filler and molded product using it |
| US20110284795A1 (en) * | 2009-01-30 | 2011-11-24 | Teijin Limited | Graphitized short fibers and composition thereof |
| JP5715884B2 (en) * | 2011-05-31 | 2015-05-13 | 住友ベークライト株式会社 | Scroll molding |
| JP2014101414A (en) * | 2012-11-16 | 2014-06-05 | Kaneka Corp | Temperature-sensitive gelation agent inclusion thermosetting resin composition |
| CN103014918B (en) * | 2012-12-14 | 2014-01-15 | 济宁碳素集团有限公司 | Method for preparing coal-series general asphalt carbon fiber |
| CN106044742B (en) * | 2016-05-30 | 2018-05-01 | 湖南大学 | A kind of preparation method of asphalt base carbon fiber self-adhesive network material |
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Non-Patent Citations (1)
| Title |
|---|
| 贺福等.超级导热型沥青基碳纤维.《高科技纤维与应用》.2003,第28卷(第5期),27－31. * |
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