CN100584881C - Carbon fiber-containing resin dispersion solution and resin composite material - Google Patents
Carbon fiber-containing resin dispersion solution and resin composite material Download PDFInfo
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- CN100584881C CN100584881C CN200480011058A CN200480011058A CN100584881C CN 100584881 C CN100584881 C CN 100584881C CN 200480011058 A CN200480011058 A CN 200480011058A CN 200480011058 A CN200480011058 A CN 200480011058A CN 100584881 C CN100584881 C CN 100584881C
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- phase growth
- dispersion
- carbon fibre
- resin
- organic solvent
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- 239000006185 dispersion Substances 0.000 title claims abstract description 96
- 239000011347 resin Substances 0.000 title claims abstract description 60
- 229920005989 resin Polymers 0.000 title claims abstract description 60
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 36
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 36
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000000463 material Substances 0.000 title claims abstract description 27
- 239000000805 composite resin Substances 0.000 title claims abstract description 19
- 239000000835 fiber Substances 0.000 claims abstract description 107
- 239000003960 organic solvent Substances 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 239000004020 conductor Substances 0.000 claims abstract description 14
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000862 absorption spectrum Methods 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 93
- 229910052799 carbon Inorganic materials 0.000 claims description 93
- 239000012071 phase Substances 0.000 claims description 81
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 70
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 48
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 21
- 239000004793 Polystyrene Substances 0.000 claims description 17
- 229920002223 polystyrene Polymers 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- -1 polyethylene terephthalate Polymers 0.000 claims description 15
- 239000004417 polycarbonate Substances 0.000 claims description 14
- 229920000515 polycarbonate Polymers 0.000 claims description 14
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 10
- 229920005575 poly(amic acid) Polymers 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 239000004642 Polyimide Substances 0.000 claims description 6
- 239000004734 Polyphenylene sulfide Substances 0.000 claims description 6
- 229920001230 polyarylate Polymers 0.000 claims description 6
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 6
- 229920001721 polyimide Polymers 0.000 claims description 6
- 229920000069 polyphenylene sulfide Polymers 0.000 claims description 6
- 238000001947 vapour-phase growth Methods 0.000 claims description 6
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 5
- 229920002492 poly(sulfone) Polymers 0.000 claims description 5
- 229920002530 polyetherether ketone Polymers 0.000 claims description 5
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004697 Polyetherimide Substances 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 229920001601 polyetherimide Polymers 0.000 claims description 3
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 3
- 238000002525 ultrasonication Methods 0.000 claims description 3
- 239000002134 carbon nanofiber Substances 0.000 abstract description 29
- 229960003237 betaine Drugs 0.000 abstract description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-O N,N,N-trimethylglycinium Chemical compound C[N+](C)(C)CC(O)=O KWIUHFFTVRNATP-UHFFFAOYSA-O 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 36
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 21
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 16
- 238000001000 micrograph Methods 0.000 description 15
- 239000011159 matrix material Substances 0.000 description 9
- 238000004528 spin coating Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000006059 cover glass Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 229920005992 thermoplastic resin Polymers 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 101100020289 Xenopus laevis koza gene Proteins 0.000 description 2
- 239000000010 aprotic solvent Substances 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- 239000004727 Noryl Substances 0.000 description 1
- 229920001207 Noryl Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- CMXPERZAMAQXSF-UHFFFAOYSA-M sodium;1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonate;1,8-dihydroxyanthracene-9,10-dione Chemical compound [Na+].O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=CC=C2O.CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC CMXPERZAMAQXSF-UHFFFAOYSA-M 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Images
Classifications
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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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
- Carbon And Carbon Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Reinforced Plastic Materials (AREA)
- Inorganic Fibers (AREA)
- Conductive Materials (AREA)
- Non-Insulated Conductors (AREA)
Abstract
The present invention provides a vapor-grown-carbon-fiber-containing dispersion containing vapor grown carbon fiber having a fiber diameter of 0.001 to 5 mum and an aspect ration of 5 to 15,000, a resin soluble in an organic solvent, and an organic solvent having an ET value of 45 or less, which value is a solvent parameter calculated from the absorption spectrum of pyridinium-N-phenol betaine, wherein (1) lumps of the carbon fiber are partially disintegrated to thereby allow individual filaments of the carbon fiber to be present as dispersed or (2) the carbon fiber is present such that carbon fiber lumps having a diameter of 40 mum or less and separated individual carbon fiber filaments are intermingled; a production method of the dispersion; vapor-grown-carbon-fiber-containing resin composite material obtained by the method; and electroconductive material and thermal conductive material using the resin composite material. The present invention enables to prepare a resin solution wherein vapor grown carbon fiber is uniformly dispersed and to easily obtain electroconductive material and thermal conductive material from the dispersed solution.
Description
The cross reference of related application
The application proposes according to 35U.S.C. the 111st (a) joint, and it is according to 35U.S.C. the 119th (e) joint (1), according to the U.S. Provisional Application No.60/467 that is specified in submission on May 2nd, 2003 of 35U.S.C. the 111st (b) joint, 155 rights and interests.
Technical field
The present invention relates to comprise the dispersion of gas-phase growth of carbon fibre.More specifically, the present invention relates to gas-phase growth of carbon fibre wherein and be evenly dispersed in the dispersion that comprises gas-phase growth of carbon fibre in the resin, relate to the method for preparing described dispersion, relate to resin composite materials by using the dispersion wherein mix gas-phase growth of carbon fibre equably to prepare, relate to the method for preparing described resin composite materials, and the purposes (as electro-conductive material or thermally conductive material) that relates to this resin composite materials.
Background technology
With carbon fiber be dispersed in matrix for example in the resin be a kind of give object electroconductibility or thermal conductivity extensively and technology commonly used.Among carbon fiber, gas-phase growth of carbon fibre is particularly useful, this is just can improve electroconductibility and thermal conductivity greatly owing to add only a spot of gas-phase growth of carbon fibre in resin, and can influence the characteristic relevant of gained resin combination and the outward appearance (Japanese Patent No.2862578 (U.S. Patent No. 5 of moulded product with processing sharply, 643,990)).
When adding carbon fiber in the resin, must mix so that carbon fiber is present in the resin equably.It is usually, described that to go in the resin be to be undertaken by the method that carbon fiber is added in the fused resin, then mediate with twin screw extruder or improved spiral tube with carbon fiber mixed.Yet, for in resin equably the blend fiber diameter be 0.001～5 μ m and staple length and the ratio (length-to-diameter ratio) of Fibre diameter is 5～15,000 vapor phase growth fine carbon in irregular shape, described melt-kneaded method can involve problem, because the fracture that needs many energy and gas-phase growth of carbon fibre can take place in kneading process.
Therefore, the inventor is devoted to prepare the dispersion in the organic solvent that fine carbon wherein is evenly dispersed in thermoplastic resin, attempts to provide the method more easily that obtains vapor phase growth fine carbon uniform mixture in resin.If can obtain the equably dispersion of fine carbon in thermoplastic resin, this dispersion can impose on object for example on the body material by coating, spraying, impregnating so, described afterwards solvent can be removed by drying, easily to prepare thermoplastic resin composition's (matrix material) thus, it has the fine carbon that is scattered in equably wherein on described matrix, and can be used as have the conduction or the thermally conductive material materials with function.
As the prior art reference of the dispersion system of relevant carbon fiber in organic solvent, Japanese Patent open (kokai) No.2002-255528 discloses the microparticle dispersion for preparing in the bipolarity aprotic solvent (methyl-sulphoxide, dimethyl formamide or acetonitrile) by fine particle is dispersed in.The carbon nanotube that has about 10nm～10 μ m sizes in this publication is used as the example of particulate and mentions.Yet, when the inventor uses that disclosed bipolarity aprotic solvent (dimethyl formamide) carries out in this publication, with regard to gas-phase growth of carbon fibre, can not obtain uniform dispersion.In addition, when gas-phase growth of carbon fibre was dispersed in the single solvent of tetrahydrofuran (THF), benzene or methylene dichloride by mechanical stirring, the initial gas-phase growth of carbon fibre piece that exists can not separate and can not produce dispersion.
Summary of the invention
Therefore, to be to provide Fibre diameter wherein be that 0.001～5 μ m and length-to-diameter ratio are that 5～15,000 gas-phase growth of carbon fibre is evenly dispersed in dispersion in the resin and preparation method thereof to one object of the present invention.
Another object of the present invention is to provide the resin composite materials that for example obtains by coating by the resin combination that uses above-mentioned dispersion of wherein mixing gas-phase growth of carbon fibre equably to prepare, its preparation method and by the above-mentioned dispersion purposes as electro-conductive material or thermally conductive material.
In view of aforementioned content, the inventor has carried out extensive studies, and have been found that comprising structural unit with at least one ring texture by employing is 45 or littler specific organic solvent as the polymkeric substance of its repeating unit as resin and ET value, can easily obtain wherein disperseing equably the resin solution of gas-phase growth of carbon fibre, and finished the present invention, wherein the ET value is solvent parameter (" Shin-jikken Kagaku Koza " (" experimental chemistry recently ") 14 (V), 2594 (1978) that the absorption spectrum by pyridine-N-phenol trimethyl-glycine calculates; Ann., 661,1 (1963)).
Therefore, the present invention relates to comprise the dispersion and its preparation method of gas-phase growth of carbon fibre, and the electro-conductive material and the thermally conductive material that relate to the resin composite materials preparation that use made by described dispersion system, as mentioned below.
1. dispersion that comprises gas-phase growth of carbon fibre, it comprises Fibre diameter is that 0.001～5 μ m and length-to-diameter ratio are 5～15,000 gas-phase growth of carbon fibre, dissolve in resin and organic solvent in the organic solvent, wherein said carbon fiber block is partly separately to make the single fiber yarn of described carbon fibre separation disperse to exist thus.
2. dispersion that comprises gas-phase growth of carbon fibre, it comprises Fibre diameter is that 0.001～5 μ m and length-to-diameter ratio are 5～15,000 gas-phase growth of carbon fibre, dissolve in resin and organic solvent in the organic solvent, wherein said carbon fiber exists so that diameter is 40 μ m or littler carbon fiber block and isolating single carbon fiber wire intermingling.
3. the dispersion that comprises gas-phase growth of carbon fibre described in 1 or 2 as mentioned, wherein said gas-phase growth of carbon fibre comprises the boron of 0.001～5 quality %.
4. arbitrary described dispersion that comprises gas-phase growth of carbon fibre in 1～3 as mentioned, the wherein said resin that dissolves in the organic solvent are to comprise to have the resin of polymkeric substance that contains the structural repeat unit of ring texture to small part.
5. arbitrary described dispersion that comprises gas-phase growth of carbon fibre in 1～4 as mentioned, the wherein said resin that dissolves in the organic solvent are any or its mixtures in polystyrene, polycarbonate, polyarylate, polysulfones, polyetherimide, polyethylene terephthalate, polyphenylene oxide, polyphenylene sulfide, polybutylene terephthalate, polyimide, polyamidoimide, polyether-ether-ketone or the polyamic acid.
6. arbitrary described dispersion that comprises gas-phase growth of carbon fibre in 1～5 as mentioned, wherein said organic solvent have 45 or littler ET value, and described ET value is the solvent parameter that the absorption spectrum by pyridine-N-phenol trimethyl-glycine calculates.
7. arbitrary described dispersion that comprises gas-phase growth of carbon fibre in 1～6 as mentioned, wherein said organic solvent has 45 or littler ET value and to have part be the cyclic structure, and described ET value is the solvent parameter that the absorption spectrum by pyridine-N-phenol trimethyl-glycine calculates.
8. arbitrary described dispersion that comprises gas-phase growth of carbon fibre in 1～7 as mentioned, wherein said organic solvent are any or its mixtures in tetrahydrofuran (THF) (THF), N-Methyl pyrrolidone, benzene, toluene, hexanaphthene, gamma-butyrolactone, the ethylene glycol butyl ether.
9. the dispersion that comprises gas-phase growth of carbon fibre described in 1 as mentioned, wherein gas-phase growth of carbon fibre and (quality) that dissolve in the resin in the organic solvent are than being " carbon fiber ": " dissolving in the resin in the organic solvent "=0.1～80: 20～99.9, and the resin content in the described dispersion is 0.1～60 quality %.
10. method for preparing the dispersion that comprises gas-phase growth of carbon fibre, it comprises that be that 0.001～5 μ m and length-to-diameter ratio are 5～15,000 gas-phase growth of carbon fibre and the gained mixture stirred and/or the step of ultrasonication with resin dissolves in organic solvent, to wherein adding Fibre diameter.
11. method for preparing the dispersion that comprises gas-phase growth of carbon fibre, it comprises that with dissolving in resin in the organic solvent and Fibre diameter be that 0.001～5 μ m and length-to-diameter ratio are that 5～15,000 vapor phase growth fine carbon mixes and the gained mixture is added step in the organic solvent.
12. a method for preparing the resin composite materials that comprises gas-phase growth of carbon fibre, it is characterized in that with as mentioned in 1～9 arbitrary described gas-phase growth of carbon fibre dispersion impose on the body material, remove described solvent afterwards.
13. a resin composite materials that comprises gas-phase growth of carbon fibre, it is by the preparation of the method described in 12 as mentioned.
14. an electro-conductive material, it comprises the resin composite materials that obtains by the method described in 12 as mentioned.
15. a thermally conductive material, it comprises the resin composite materials by method obtains described in 12 as mentioned.
The carbon fiber that can be used among the present invention is that Fibre diameter is that 0.001 μ m～5 μ m and length-to-diameter ratio are 5～15,000 gas-phase growth of carbon fibre.The preferred embodiment of described carbon fiber comprises the carbon fiber from vapor phase growth, and this fiber can prepare (referring to Japanese Patent No.2778434) together with iron or analogous element as catalyzer by winding-up gaseous organic compound under hot environment.
Described carbon fiber by vapor phase growth (gas-phase growth of carbon fibre) for example can be " (the as produced) of former state preparation " carbon fiber; By the carbon fiber that obtains at 800～1500 ℃ of following thermal treatments " the former state preparation " carbon fiber; Perhaps by under 2000～3000 ℃, making the carbon fiber that " former state prepares ", carbon fiber and graphiteization obtained.Preferably, under 1500 ℃ described gas-phase growth of carbon fibre is being heat-treated or under 2000 ℃～3000 ℃, making its greying before use.
In the graphitizing process, can for example B, Al, Be or Si, preferred B add in the described gas-phase growth of carbon fibre with promoting carbon crystalline element, to prepare gas-phase growth of carbon fibre thus, the crystallization that the carbon crystal of wherein said fiber contains on a small quantity (0.001～5 quality %, preferred 0.01～2 quality %) promotes element (WO00/585326).
Being ready to use in the resin that forms dispersion of the present invention can be the resin of thermoplastic resin, thermosetting resin or any other type, as long as it dissolves in the organic solvent.The described resin that dissolves in the organic solvent can be to comprise to have the resin of polymkeric substance that contains the structural repeat unit of ring texture to small part.Described ring texture can also comprise oxygen, nitrogen or sulphur atom except carbon atom.
The example of described resin comprises polystyrene, polycarbonate (PC), polyarylate (PAR), polysulfones, polyethers-imide, EOT (polyethylene sulfide), polyphenylene sulfide (PPS), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyimide, polyamidoimide, polyether-ether-ketone, Noryl and polyamic acid.The preferred embodiment of described resin comprises polystyrene, polycarbonate, polyarylate, polysulfones, polyethers-imide, EOT, polyphenylene sulfide, polybutylene terephthalate, polyimide, polyamidoimide, polyether-ether-ketone, polyamic acid and composition thereof.
Gas-phase growth of carbon fibre changes according to the desired use of described resin composite materials with (quality) beguine that dissolves in the resin in the organic solvent.Usually, this ratio (being carbon fiber: dissolve in the resin in the organic solvent) is 0.1: 99.9～80: 20, and the resin content of described dispersion is 0.1～60 quality %.When the amount of gas-phase growth of carbon fibre is less than 0.1 quality %, after removing, solvent can not obtain gratifying electroconductibility of described composition or thermal conductivity, otherwise it is when the amount of fiber surpasses 80 quality %, frangible often by the cold coating composition that described resin dispersion obtains.
The organic solvent that is used as dispersion medium among the present invention preferably has 45 or littler ET value, described ET value is solvent parameter (" Shin-jikken Kagaku Koza " (" new experimental chemistry ") 14 (V), 2594 (1978) that the absorption spectrum by pyridine-N-phenol trimethyl-glycine calculates; Ann., 661,1 (1963)).The preferred embodiment of described solvent comprises methylene dichloride, chloroform, glycol dimethyl ether, ethyl acetate, bromobenzene, chlorobenzene, tetrahydrofuran (THF) (THF), methyl-phenoxide, diox, diethyl ether, benzene, tetracol phenixin, toluene, hexanaphthene, hexane and octane-iso.Preferred solvent has ring texture, and the example comprises tetrahydrofuran (THF) (THF), N-Methyl pyrrolidone, benzene, toluene, hexanaphthene and gamma-butyrolactone.
Ratio for gas-phase growth of carbon fibre, resin (solute) and dispersion medium has no particular limits.Preferably, described solute resin is sneaked into to help dispersion with 60 quality % or littler amount.
Have no particular limits for described dispersing method.For example, by with resin dissolves in organic solvent, to wherein adding gas-phase growth of carbon fibre and then this mixture being stirred or ultrasonication, can prepare stable dispersion.
The state of dispersion is according to the situation of gas-phase growth of carbon fibre and difference.Usually, before being disperseed, the single fiber yarn of gas-phase growth of carbon fibre is not separated from each other.But its aggregate as the about 100 μ m of diameter exists.When by the inventive method described gas-phase growth of carbon fibre being disperseed, the single fiber yarn of described gas-phase growth of carbon fibre is separated from one another in dispersions obtained.Perhaps, dispersions obtainedly can comprise about 40 μ m of the diameter separately that is in mutual admixture or littler aggregate and single carbon fiber wire.
With wherein adding Fibre diameter with the amount of 5 quality % is that 0.15 μ m and length-to-diameter ratio are 70 and 2, sneak into benzene (BZ through the polycarbonate as resin of heat treated gas-phase growth of carbon fibre down for 800 ℃, ET value=34.5), tetrahydrofuran (THF) (THF, ET value=37.4), methylene dichloride (DCM, ET value=41.1), dimethyl formamide (DMF, ET value=43.8) or acetonitrile (ATN, ET value=46.0) in, to prepare 10 quality % dispersions of described resin thus, stirred 30 minutes with agitator afterwards.Under described organic solvent is situation any in benzene, tetrahydrofuran (THF), methylene dichloride and the dimethyl formamide, even the dispersion that comprises gas-phase growth of carbon fibre of gained also can not cause the precipitation of gas-phase growth of carbon fibre after placing a week.Contrast is under the situation of acetonitrile at described organic solvent, and the dispersions obtained precipitation that just began at second day produces limpid supernatant liquor.
By coating drying means (after wherein applying, making wherein contained solvent evaporation) dispersion of the present invention is imposed on last the making of matrix (for example circuit card) and can obtain the wherein homodisperse resin composite materials of gas-phase growth of carbon fibre by drying.The material that so obtains has been endowed outstanding electroconductibility and thermal conductivity.For dispersion of the present invention is imposed on the matrix, can adopt the ordinary method that applies mashed prod or dispersion; For example, coating can form by using scraper, silk screen printing or spin coating.For the solvent of the described coating of drying, can be usually used in the ordinary method of evaporating solvent, for example heat drying and vacuum-drying.
The accompanying drawing summary
Fig. 1 (A) and 1 (B) are respectively the light micrograph figure of the PS/THF base dispersion of basic dispersion of the PC/THF of VGCF and VGCF.
Fig. 2 (A) and 2 (B) are respectively the light micrograph figure of the film that forms of spin coating that the spin coating of the PC/THF base dispersion by VGCF forms and the PS/THF base dispersion by VGCF.
Fig. 3 (A) and 3 (B) are respectively the light micrograph figure of the PS/DMF base dispersion of basic dispersion of the PS/BZ of VGCF and VGCF.
Fig. 4 (A) and 4 (B) are respectively the light micrograph figure of the film that forms of spin coating that the spin coating of the PS/BZ base dispersion by VGCF forms and the PS/DMF base dispersion by VGCF.
Fig. 5 is the light micrograph figure of the dispersion of VGCF in the mixing solutions of polyamic acid/N-N-methyl-2-2-pyrrolidone N-, gamma-butyrolactone and ethylene glycol butyl ether.
Fig. 6 (A) and 6 (B) are respectively the light micrograph figure of VGCF in THF (A) and the dispersion in DCM (B).
Fig. 7 (A) and 7 (B) are respectively the light micrograph figure of VGCF in BZ (A) and the dispersion in DMF (B).
Fig. 8 is the light micrograph figure of the PS/ATN base dispersion of VGCF.
Fig. 9 is the light micrograph figure of the PMMA/THF base dispersion of VGCF.
Implement best mode of the present invention
To describe the present invention by embodiment and comparative example below, it should not be interpreted as limitation of the present invention.
Embodiment 1:
Preparation polycarbonate (PC; The product of Teijin Chemicals Ltd., AD5503; Number-average molecular weight=20,000, weight-average molecular weight=32,000) 10 quality % solution in tetrahydrofuran (THF) (THF).Adding Fibre diameter with the amount of 0.2 quality % in described solution is 0.15 μ m and length-to-diameter ratio 70 and 2,800 ℃ are experienced heat treated gas-phase growth of carbon fibre (VGCF down, registered trademark, the product of Showa Denko K.K.), then stirred 30 minutes with 600rpm with mechanical stirrer.Obtain the homodisperse dispersion of wherein said gas-phase growth of carbon fibre.After this dispersion is at room temperature placed 7 days, do not observe the precipitation of gas-phase growth of carbon fibre.Observation under opticmicroscope confirms that the single fiber yarn of VGCF (registered trademark) is disperseed quite with flying colors.By several described dispersions are imposed on the cover glass and with 100rpm rotate this cover glass 5 seconds, with 1, the film of matrix material is made in 000rpm rotation 10 seconds and with 100rpm rotation 5 seconds and carry out spin coating thus.Find that the gained film comprises outstanding dispersive VGCF (registered trademark).
Similarly, prepare film by using dispersion and described spin coating method, different is with polystyrene (PS; The product of Asahi Kasei, PS666, number-average molecular weight=420,000, weight-average molecular weight=1,000,000) used polycarbonate (PC) above the replacement.Fig. 1 and 2 shows dispersions obtained and light micrograph figure film.
Embodiment 2:
The combination of used polystyrene (PS) and THF changes to and uses benzene (BZ) or dimethyl formamide (DMF) to replace THF among the embodiment 1, to prepare dispersion thus and and to form film by spin coating.
Fig. 3 and 4 shows the light micrograph figure of dispersions obtained and film.
Embodiment 3:
In by the solvent made from mixed N-N-methyl-2-2-pyrrolidone N-, gamma-butyrolactone and the ethylene glycol butyl ether of 30: 30: 35 quality %, by preparing solution to wherein adding and dissolving 5 quality % polyamic acids (it is the precursor of polyimide).Amount in polymkeric substance 2 quality % or 5 quality % in described solution adds VGCF (registered trademark), then stirs 20 minutes with 200rpm with magnetic stirring apparatus.This mixture was at room temperature placed 7 days.The dispersion that discovery contains the dispersion of 2 quality %VGCF (registered trademark) and contains 5 quality %VGCF (registered trademark) does not all have the precipitation of gas-phase growth of carbon fibre.Observation under opticmicroscope confirms that the single fiber yarn of VGCF (registered trademark) is disperseed quite with flying colors.This light micrograph is shown among Fig. 5.By several described dispersions are imposed on the cover glass and with 100rpm rotate this cover glass 5 seconds, with 1,000rpm rotation 10 seconds and with 100rpm rotation 5 seconds, thus form the film of matrix material via spin coating.Find that the gained film comprises outstanding dispersive VGCF (registered trademark).
Embodiment 4:
The dispersion that comprises gas-phase growth of carbon fibre that makes among the embodiment 1 is applied on the circuit card matrix by silk screen printing, uses dry air then, comprise the filming of matrix material of gas-phase growth of carbon fibre with preparation thus.Estimate the electroconductibility of this film (estimating embodiment No.1).Respectively, the amount by change polycarbonate as shown in table 1 and gas-phase growth of carbon fibre forms film (estimating embodiment No.2-4).In addition, by using polystyrene (PS; The product of Asahi Kasei, PS666, number-average molecular weight=420,000, weight-average molecular weight=1,000,000) replace polycarbonate, form another and film, and estimate the electroconductibility of gained sample (estimating embodiment No.5).It the results are shown in the table 1.
Comparative example 1:
VGCF is added in tetrahydrofuran (THF) (THF), methylene dichloride (DCM), benzene (BZ) and each solvent of dimethyl formamide (DMF), with VGCF (registered trademark) concentration that reaches 0.2 quality %.Stirred each mixture 30 minutes with mechanical stirrer with 600rpm, to obtain dispersion thus.Described dispersion is clipped between slide glass and the cover glass, and is placed on the dispersion state of observing VGCF (registered trademark) under the opticmicroscope with * 400 magnification.Still observe VGCF (registered trademark) piece of initial existence.After described dispersion is at room temperature placed, observed the precipitation of gas-phase growth of carbon fibre in second day.Fig. 6 and 7 shows the light micrograph figure of described dispersion.
Comparative example 2:
Replace used solvent THF among the embodiment 2 with acetonitrile (ATN), to prepare dispersion thus.Fig. 8 shows the light micrograph figure of this dispersion.
Comparative example 3:
With polymethylmethacrylate (PMMA; The product of Asahi Kasei, 60N, number-average molecular weight=76,000, weight-average molecular weight=150,000) replace used resin PC among the embodiment 1, to prepare dispersion thus.Fig. 9 shows the light micrograph figure of this dispersion.
Table 1
Industrial applicability
Be that 0.001～5 μ m and draw ratio are 5～15,000 vapor grown carbon by using fibre diameter Fiber, dissolve in the resin in the organic solvent and have 45 or the non-polar solven of littler ET value As organic solvent, wherein said ET value is the absorption spectrum calculating by pyridine-N-phenol betaine The solvent parameter that goes out, the present invention can prepare the wherein homodisperse resin solution of gas-phase growth of carbon fibre. For example can easily obtain conductive material and Heat Conduction Material by applying by described dispersion.
Claims (17)
1. dispersion that comprises gas-phase growth of carbon fibre, it is that 0.001～5 μ m and length-to-diameter ratio are 5～15 by Fibre diameter, 000 gas-phase growth of carbon fibre, dissolve in the resin in the organic solvent and have 45 or the organic solvent composition of littler ET value, described ET value is the solvent parameter that the absorption spectrum by pyridine-N-phenol trimethyl-glycine calculates, the described resin that dissolves in the organic solvent is a polystyrene, polycarbonate, polyarylate, polysulfones, polyetherimide, polyethylene terephthalate, polyphenylene oxide, polyphenylene sulfide, polybutylene terephthalate, polyimide, polyamidoimide, in polyether-ether-ketone or the polyamic acid any, or its mixture, wherein said carbon fiber block is partly separated, and makes isolating single carbon fiber wire exist dispersedly thus.
2. the dispersion that comprises gas-phase growth of carbon fibre described in claim 1, wherein said gas-phase growth of carbon fibre comprises the boron of 0.001～5 quality %.
3. the dispersion that comprises gas-phase growth of carbon fibre described in claim 1, the wherein said resin that dissolves in the organic solvent are to comprise to have the resin of polymkeric substance that contains the structural repeat unit of ring texture to small part.
4. the dispersion that comprises gas-phase growth of carbon fibre described in claim 1, wherein said organic solvent has 45 or littler ET value and to have part be the cyclic structure, and described ET value is the solvent parameter that the absorption spectrum by pyridine-N-phenol trimethyl-glycine calculates.
5. the dispersion that comprises gas-phase growth of carbon fibre described in claim 1, wherein said organic solvent are any or its mixtures in tetrahydrofuran (THF), N-Methyl pyrrolidone, benzene, toluene, hexanaphthene, gamma-butyrolactone, the ethylene glycol butyl ether.
6. the dispersion that comprises gas-phase growth of carbon fibre described in claim 1, wherein gas-phase growth of carbon fibre is " carbon fiber " with the mass ratio that dissolves in the resin in the organic solvent: " dissolving in the resin in the organic solvent "=0.1～80: 20～99.9, and the resin content in the described dispersion is 0.1～60 quality %.
7. dispersion that comprises gas-phase growth of carbon fibre, it is that 0.001～5 μ m and length-to-diameter ratio are 5～15 by Fibre diameter, 000 gas-phase growth of carbon fibre, dissolve in the resin in the organic solvent and have 45 or the organic solvent composition of littler ET value, described ET value is the solvent parameter that the absorption spectrum by pyridine-N-phenol trimethyl-glycine calculates, the wherein said resin that dissolves in the organic solvent is a polystyrene, polycarbonate, polyarylate, polysulfones, polyetherimide, polyethylene terephthalate, polyphenylene oxide, polyphenylene sulfide, polybutylene terephthalate, polyimide, polyamidoimide, in polyether-ether-ketone or the polyamic acid any, or its mixture, the existence of wherein said carbon fiber makes that diameter is 40 μ m or littler carbon fiber block and isolating single carbon fiber wire intermingling.
8. the dispersion that comprises gas-phase growth of carbon fibre described in claim 7, wherein said gas-phase growth of carbon fibre comprises the boron of 0.001～5 quality %.
9. the dispersion that comprises gas-phase growth of carbon fibre described in claim 7, the wherein said resin that dissolves in the organic solvent are to comprise to have the resin of polymkeric substance that contains the structural repeat unit of ring texture to small part.
10. the dispersion that comprises gas-phase growth of carbon fibre described in claim 7, wherein said organic solvent has 45 or littler ET value and to have part be the cyclic structure, and described ET value is the solvent parameter that the absorption spectrum by pyridine-N-phenol trimethyl-glycine calculates.
11. the dispersion that comprises gas-phase growth of carbon fibre described in claim 7, wherein said organic solvent are any or its mixtures in tetrahydrofuran (THF), N-Methyl pyrrolidone, benzene, toluene, hexanaphthene, gamma-butyrolactone, the ethylene glycol butyl ether.
12. method for preparing according to the dispersion that comprises gas-phase growth of carbon fibre of claim 1 or 7, it comprises that be that 0.001～5 μ m and length-to-diameter ratio are 5～15,000 gas-phase growth of carbon fibre and the gained mixture stirred and/or the step of ultrasonication with resin dissolves in organic solvent, to wherein adding Fibre diameter.
13. method for preparing according to the dispersion that comprises gas-phase growth of carbon fibre of claim 1 or 7, it comprises that with dissolving in resin in the organic solvent and Fibre diameter be that 0.001～5 μ m and length-to-diameter ratio are that 5～15,000 vapor phase growth fine carbon mixes and the gained mixture is added step in the organic solvent.
14. a method for preparing the resin composite materials that comprises gas-phase growth of carbon fibre is characterized in that removing described solvent afterwards with imposing on the body material as each described gas-phase growth of carbon fibre dispersion in the claim 1～11.
15. a resin composite materials that comprises gas-phase growth of carbon fibre, it is by the preparation of the method described in claim 14.
16. an electro-conductive material, it comprises the resin composite materials that obtains by the method described in claim 14.
17. a thermally conductive material, it comprises the resin composite materials that obtains by the method described in claim 14.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP120617/2003 | 2003-04-24 | ||
| JP2003120617 | 2003-04-24 |
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| CN100584881C true CN100584881C (en) | 2010-01-27 |
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| CN200480011058A Expired - Lifetime CN100584881C (en) | 2003-04-24 | 2004-04-23 | Carbon fiber-containing resin dispersion solution and resin composite material |
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| Country | Link |
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| JP (1) | JP2010242091A (en) |
| KR (1) | KR101122610B1 (en) |
| CN (1) | CN100584881C (en) |
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| DE (1) | DE602004011042T2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2004339485A (en) * | 2003-04-24 | 2004-12-02 | Showa Denko Kk | Carbon fiber-containing resin dispersion, and resin composite material |
| TWI405667B (en) * | 2010-12-15 | 2013-08-21 | Ind Tech Res Inst | Polyimide film laminate and metal laminate employing the same |
| CN102604300A (en) * | 2012-03-15 | 2012-07-25 | 东营帕瓦电力技术有限公司 | Nano crystal lipid special material |
| US9631067B2 (en) | 2012-08-22 | 2017-04-25 | Korea Institute Of Ceramic Engineering And Technology | Carbon fiber composite coated with silicon carbide and production method for same |
| JP2014154459A (en) * | 2013-02-13 | 2014-08-25 | Nippon Zeon Co Ltd | Conductive film, gas diffusion layer for fuel cell, catalyst layer for fuel cell, electrode for fuel cell, membrane electrode assembly for fuel cell, fuel cell, and method for manufacturing membrane electrode assembly for fuel cell |
| CN105838052A (en) * | 2015-01-16 | 2016-08-10 | 汉达精密电子(昆山)有限公司 | Carbon fiber reinforced polycarbonate composite material and product thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0639576B2 (en) * | 1985-03-23 | 1994-05-25 | 旭化成工業株式会社 | Carbonaceous fiber-containing coating composition |
| JPS6243006A (en) * | 1985-08-19 | 1987-02-25 | 昭和電工株式会社 | Making of conducting high polymer material |
| JPS62119269A (en) * | 1985-11-20 | 1987-05-30 | Mitsubishi Chem Ind Ltd | Electrically conductive resin composition |
| JP2862578B2 (en) * | 1989-08-14 | 1999-03-03 | ハイピリオン・カタリシス・インターナシヨナル・インコーポレイテツド | Resin composition |
| JP3188283B2 (en) * | 1991-05-21 | 2001-07-16 | 昭和電工株式会社 | Liquid absorbent |
| JPH06122785A (en) * | 1991-12-10 | 1994-05-06 | Nikkiso Co Ltd | Conductive composition, conductive coating material, conductive ink, and electric circuit board |
| JPH07102197A (en) * | 1993-09-10 | 1995-04-18 | Hyperion Catalysis Internatl Inc | Coating composition |
| JPH09115334A (en) * | 1995-10-23 | 1997-05-02 | Mitsubishi Materiais Corp | Transparent conductive film and composition for film formation |
| EP1191131B1 (en) * | 1999-03-25 | 2006-12-20 | Showa Denko Kabushiki Kaisha | Carbon fiber, method for producing the same and electrode for cell |
| JP3708390B2 (en) * | 2000-01-20 | 2005-10-19 | 昭和電工株式会社 | Conductive thermoplastic resin composition |
| JP3606782B2 (en) * | 2000-01-21 | 2005-01-05 | 昭和電工株式会社 | Conductive paint |
| JP2002255528A (en) * | 2000-09-18 | 2002-09-11 | Matsushita Electric Ind Co Ltd | Fine particle dispersed liquid and its producing method |
| JP2002134115A (en) * | 2000-10-23 | 2002-05-10 | Takiron Co Ltd | Conductive binder liquid for lithium ion secondary battery, method of preparing binder liquid and electrode material for lithium ion secondary battery using binder liquid |
| DE60143954D1 (en) * | 2000-12-20 | 2011-03-10 | Showa Denko Kk | BRANCHED, STEAM-GROUNDED CARBON FIBER, AND ITS USE |
| JP4342929B2 (en) * | 2002-12-26 | 2009-10-14 | 昭和電工株式会社 | Carbonaceous material for conductive composition and use thereof |
| JP4261956B2 (en) * | 2003-03-31 | 2009-05-13 | ニチアス株式会社 | Conductive resin, composition for conductive resin, and production method thereof |
| JP2004339485A (en) * | 2003-04-24 | 2004-12-02 | Showa Denko Kk | Carbon fiber-containing resin dispersion, and resin composite material |
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| 气相生长碳纤维. 陈久岭.天然气化工，第23卷第2期. 1998 |
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| Publication number | Publication date |
|---|---|
| DE602004011042D1 (en) | 2008-02-14 |
| CN1777639A (en) | 2006-05-24 |
| KR101122610B1 (en) | 2012-03-15 |
| DE602004011042T2 (en) | 2009-01-02 |
| ATE382658T1 (en) | 2008-01-15 |
| KR20060013512A (en) | 2006-02-10 |
| JP2010242091A (en) | 2010-10-28 |
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