CN100556956C - Conductive polymers and its production and use - Google Patents
Conductive polymers and its production and use Download PDFInfo
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- CN100556956C CN100556956C CNB2004800252327A CN200480025232A CN100556956C CN 100556956 C CN100556956 C CN 100556956C CN B2004800252327 A CNB2004800252327 A CN B2004800252327A CN 200480025232 A CN200480025232 A CN 200480025232A CN 100556956 C CN100556956 C CN 100556956C
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Abstract
The invention provides a kind of production method of conductive polymers, be included in 1,000mJ/m
2Or under the lower mixing energy, will be at 100s
-1Be in melt viscosity under the shearing rate and be the step of the vapor-grown carbon fibers blend of the polymkeric substance of 600Pas or lower state and 1-15 quality %, and the conductive polymers that obtains thus.Preferably, used vapor-grown carbon fibers has fiber external diameter, the 40-1 of 80-500nm, 000 length-to-diameter ratio, 4-30m
2The BET specific surface area of/g, the 0.345nm that obtains by the X-ray diffraction method or littler d
002, according to (Id/Ig) ratio of raman scattering spectrum 0.1-2, wherein Id and Ig represent 1 separately, 341-1,349cm
-1With 1,570-1,578cm
-1The peak height of band.According to the present invention, by to obtain excellent electroconductibility than the amount mixed vapour grown carbon fiber that lacks in the ordinary method.
Description
The cross reference of related application
The application is the application of submitting to according to 35U.S.C. § 111 (a) money, according to 35U.S.C. § 119 (e) (1), the provisional application of submitting on September 5th, 2003 according to 35U.S.C. § 111 (b) 60/500 is enjoyed in requirement, the right of the applying date of the provisional application 60/546,973 that on February 24th, 237 and 2004 submitted to.
Technical field
The present invention relates to a kind of with the production method of vapor-grown carbon fibers as the conductive polymers of conductive filler material, the production method that more specifically relates to a kind of conductive polymers, be mixed with more a spot of vapor-grown carbon fibers in this polymkeric substance, but show higher electroconductibility high equally with conventional conductive polymers or that compare.And, the present invention relates to by the physical strength with excellence of this method production and the conductive polymers of electroconductibility, and relate to the purposes of this polymkeric substance.
Background technology
Usually, it is a kind of well known technology for a long time that the thermoplastic resin of electrical isolation own is mixed with conductive filler material, be used to give the characteristic resin such as electroconductibility and the static resistance, thereby many conductive filler materials is used for this purpose.
When conducting material being incorporated into the resin that is generally isolator or rubber in order to give electroconductibility, observe so a kind of phenomenon, promptly sharply increase on the point of electroconductibility when this addition reaches critical amount that when the loading level of conducting material increases, only increases gradually, and then increase gradually, so-called " puncturing (percolation) ", the feature from the isolator to the conductor changes.This is construed as, and the three-dimensional network that formed in isolator matrix by electric conductor causes.Critical amount is called " breakdown threshold (percolation thresold) " (being designated hereinafter simply as " threshold value ").Known this threshold value in fact depends on the type of the resin that serves as matrix and the type of conductor.
Usually the example of the conductive filler material that adopts comprises the carbonaceous material with graphite-structure, for example carbon black, graphite, vapor-grown carbon fibers (below be abbreviated as " CF ") and carbon fiber; Metallic substance, for example steel fiber, metal-powder and tinsel; Metal oxide; And the mineral filler that scribbles metal.Wherein, in order to obtain high conductivity, encourage to use carbon black or hollow carbon fiber by mixing a small amount of conductive filler material.
Yet, when the amount that increases conductive filler material when obtaining high conductivity, the melt fluidity of aforementioned resin reduces, and causes difficulty and be easy to cause reinforced not enough in molded.Even when molded finishing, moulded product presents appearance of poor quality.In addition, can generate moulded product unsatisfactory (showing each reinforced quality fluctuation and the poor mechanical properties such as shock strength).Thus, in order to increase by adding the electroconductibility that a small amount of conductive filler material obtains, studied the electroconductibility (for example, referring to the open 2001-200096 of Japanese patent application) that increases filler itself.
(rely in the conductive resin composition by the forming of conductive network that forms by conductive filler material and, mainly studied following three kinds of methods reducing threshold value by uprising in conjunction with conductive filler material on a small quantity and becoming in the stable trial in this electroconductibility.
I) to the research of the influence of conductive filler material shape
The surface-area by the size of dwindling conductive filler material, the length-to-diameter ratio that increases filler or increase filler has been illustrated in this research, can reduce threshold value.
Ii) for the research of mixed with polymers technology
For the blending resin that has sea-island structure or mutual continuous structure in the microtexture, it was suggested a kind of formation carbon black matrix resin method for compositions, wherein by carbon black is sneaked into (for example, referring to the open 02-201811 of Japanese patent application) in the marine facies compatible with carbon black (being matrix phase or the external phase) resin equably with high density and high-density.
Another kind of formation CF matrix resin method for compositions has also been proposed, wherein by CF is sneaked into (for example, referring to the open 01-263156 of Japanese patent application) in the marine facies compatible with CF (being matrix phase or the external phase) resin equably with high density and high-density.
Iii) by improving the method that interfacial energy reduces threshold value
Be illustrated in the composite composition of any various resin and carbon black, interfacial energy is big more, threshold value more little (for example, in the situation of polypropylene/carbon black, interfacial energy is than high in nylon/carbon black situation, and threshold value is just lower).When with carbon black when the conductive filler material, attempted improving black carbon surface and can improve interfacial energy between carbon black and the resin by oxide treatment.
Aforementioned research is extensively carried out, stably to reduce threshold value by polymer blending method and other method by the electroconductibility that improves conductive filler material.Yet, change in unacceptable situation at the parent material intrinsic property that causes by polymer blending, can not use the polymer blending method.When the shape of cutting apart conductive filler material attenuates or the length-to-diameter ratio of filler or surface-area when increasing, prevent the flowability of composition during molded, to suffer damage.To reduce the effect of method of threshold value not remarkable by increasing interfacial energy.Like this, when obtaining to comprise the highly conductive resin composition of single resin system, still leave over mobilely during the physical property qualitative change is bad, molded reduce, the problem of moulded product outward appearance of poor quality.
Especially, along with size in office automation (OA) equipment and the electronics is dwindled, integrated and precision development of technology, the commerce that adheres to minimum value of reduction dust on electricity/electronic package need increase and is increasing year by year.
For example, this need be stronger in following field, promptly be used for semiconductor element IC chip, wafer, be used for the internals of hard disc of computer etc., and must be by giving the member static resistance crookedly prevent the adhesion of dust on these members.Be this type of application, as conductive resin composition, polycarbonate resin (making polycarbonate resin and ABS resin blend) that mainly contains polymer alloy or the polyphenylene oxide resin (making polyphenylene oxide resin and polystyrene resin blend) that mainly contains polymer alloy have been adopted, to wherein sneaking into conductive filler material, for example carbon black.In order to obtain high conductivity, a large amount of carbon blacks must be incorporated in the resin, cause the physical strength and the mobile problem that reduce electroconductive resin.
For the automobile external member, in the moulded product energising, the coating spraying that is added with opposite charges on it part to the resin formed article of giving electroconductibility applies by " electrostatic coating ".In the electrostatic coating method, based on the magnetism between the opposite charges in lip-deep electric charge and the coating, coating is reinforced to the adhesion on the molded article surface.Many outside plates of automobile and parts all are made of polycarbonate resin-polyester co-mixture or poly (phenylene ether)-polyamide resin blends thing.Sneak in these molded resin materials when giving electroconductibility when conductive filler material, its physical strength and flowability reduce unfriendly.
Summary of the invention
An object of the present invention is to provide a kind of production method of conductive polymers, this method is by obtaining higher electroconductibility identical with conventional conductive polymers or that compare with vapor-grown carbon fibers as conductive filler material, and conductive filler material is sneaked into the amount of lacking than routine employing amount, thus can keep physical strength and when preventing to mediate viscosity increase; The conductive polymers that a kind of method thus obtains and the purposes of this polymkeric substance.
The inventor has been found that, for to obtain the electroconductibility identical or higher with conventional polymer than the vapor-grown carbon fibers mixed volume that lacks in the ordinary method, importantly show under the condition of the melt viscosity under the set-point by adopting the low blend can be, and finish the present invention based on this discovery with polymkeric substance and carbon fiber blend at polymkeric substance.
Thereby, the invention provides a kind of conductive polymers, and the method for producing this polymkeric substance.
1. a method of producing conductive polymers is included in 1,000mJ/m
3Or under the lower mixing energy, will be at 100s
-1Be in melt viscosity under the shearing rate and be the step of the vapor-grown carbon fibers blend of the polymkeric substance of 600Pas or lower state and 1-15 quality %.
2. the method for the production conductive polymers described in project 1, wherein polymkeric substance is at 100s
-1Be in melt viscosity under the shearing rate and be the uncured thermosetting polymer of 200Pas or lower state, and blend is at 400mJ/m
3Or carry out under the lower mixing energy.
3. the method for the production conductive polymers described in project 1, wherein polymkeric substance is at 100s
-1Be in the thermoplastic polymer that melt viscosity is the state of 200-600Pas under the shearing rate, and blend is at 200-1,000mJ/m
3Mixing energy under carry out.
4. as the method for each described production conductive polymers among the project 1-3, wherein vapor-grown carbon fibers has fiber external diameter, the 40-1 of 80-500nm, 000 length-to-diameter ratio, 4-30m
2The BET specific surface area of/g, the 0.345nm that obtains by the X-ray diffraction method or littler d
002, 0.1-2 (Id/Ig) ratio, wherein Id represents 1,341-1,349cm
-1The peak height of band, Ig represents 1,570-1,578cm
-1The peak height of band, these bands are observed in raman scattering spectrum.
5. as the method for each described production conductive polymers among the project 1-4, wherein vapor-grown carbon fibers has passed through in inert atmosphere 2,000-3,500 ℃ thermal treatment.
6. as the method for each described production conductive polymers among the project 1-5, wherein vapor-grown carbon fibers has 115mJ/m
2Or lower surface energy.
7. the method for the production conductive polymers described in project 6, wherein vapor-grown carbon fibers through wet method or dry process to reduce surface energy.
8. the method for the production conductive polymers described in project 7 is wherein in order to reduce being treated to fluoridation, adding that boron is handled or silanization is handled of surface energy.
9. the method for the production conductive polymers described in project 2, wherein thermosetting polymer is selected from polyethers, polyester, polyimide, polysulfones, Resins, epoxy, unsaturated polyester resin, phenol resins, urethane resin, ureic resin and melamine resin.
10. the method for the production conductive polymers described in project 3, wherein thermoplastic polymer is selected from polymeric amide, polyester, liquid crystalline polymers, polyethylene, polypropylene, polyphenylene sulfide and polystyrene.
11. a method of producing conductive polymers comprises at 100s
-1The polymkeric substance and the surface energy that are in melt viscosity under the shearing rate and are 600Pas or lower state are 115mJ/m
2Or the step of lower vapor-grown carbon fibers blend.
12. the production conductive polymers method described in project 11, wherein polymkeric substance is selected from least a in thermoplastic resin and the thermosetting resin.
13. the production method of the conductive polymers described in project 11 or 12, wherein vapor-grown carbon fibers has passed through wet method or dry process to reduce surface energy.
14. as the production method of each described conductive polymers among the project 11-13, wherein vapor-grown carbon fibers has 5 μ m or littler fiber diameter.
15. the production conductive polymers method described in project 13 is wherein in order to reduce being treated to fluoridation, adding that boron is handled or silanization is handled of surface energy.
16. a conductive polymers is by being obtained by each described production method among the project 1-15.
17. a moulded product, the conductive polymers that is obtained by each described production method among the project 1-15 constitutes.
18. an outside appurtenances that is used for automobile uses the conductive polymers that is obtained by each described production method among the project 1-15.
19. an electromagnetic shielding material uses the conductive polymers that is obtained by each described production method among the project 1-15.
20. an antistatic material adopts the conductive polymers that is obtained by each described production method among the project 1-15.
21. a conductive adhesion material uses the conductive polymers that is obtained by each described production method among the project 1-15.
Detailed Description Of The Invention
Next the present invention will be described in further detail.
The vapor-grown carbon fibers that adopts among the present invention can be produced in the thermolysis in the presence of the organo-transition metal compound by organic compound.
The example that can be used as the organic compound of producing the vapor-grown carbon fibers raw material comprise the toluene of gas form, benzene, naphthalene, ethene, acetylene, ethane, Sweet natural gas, carbon monoxide and composition thereof.Wherein, the preferred aromatic hydrocarbon such as toluene and benzene.
Used organo-transition metal compound contains the transition metal that serves as catalyzer during the organic compound thermolysis among the present invention.The example of contained transition metal comprises the metallic element of 4-10 family in the periodic table of elements in the organo-transition metal compound.The preferred especially compound such as ferrocene or nickelocene.
By aforesaid organic compound and aforesaid organo-transition metal compound are mixed with reducing gas such as hydrogen, and this mixture is infeeded the Reaktionsofen that is heated to 800-13000 ℃, cause that thus thermolysis produces vapor-grown carbon fibers.
So the vapor-grown carbon fibers of producing can be a hollow along fibre axis, but perhaps fiber bifurcated.In order to improve the consistency of fiber and matrix resin, preferably by in inert atmosphere in 900-1, vapor-grown carbon fibers is cured in the thermal treatment under 300 ℃, removes thus at the organic substance such as tar that can adhere to during the production stage on the fiber.Especially, in order to increase the intrinsic conductivity of vapor-grown carbon fibers, preferably in inert atmosphere in 2,000-3,500 ℃ of following further thermal treatment vapor-grown carbon fibers, growth is contained in the graphite crystal in the vapor-grown carbon fibers thus.When the thermal treatment not necessarily of vapor-grown carbon fibers quilt, can and be molded as solid pressed compact (for example column pressed compact) with the fiber extruding.
Do not have particular restriction for being used for the heat treated stove of pressed compact, can adopt any stove such as typical Acheson type stove, resistance furnace or high frequency furnace, as long as this stove can keep 2,000 ℃ or higher, preferred 2,300 ℃ or higher target temperature get final product.In addition, can heat pressed compact by direct energising.After heating is finished, slight broken or pulverize this compressing tablet, to particulate carbon fiber product (fiber external diameter: 80-500nm, length-to-diameter ratio: 40-1,000, BET specific surface area: 4-30m are provided thus
2/ g).
2,000 ℃ or more relative superiority or inferiority to carry out aforementioned heat treated atmosphere be nonoxidizing atmosphere, preferably contain the rare gas atmosphere that one or more are selected from materials such as argon, helium, neon.Heat treatment period is preferably short as much as possible from productivity.When carbon fiber was heated the long period, fiber sintering solidified, and reduces productive rate thus.Thereby, after the temperature in the pressed compact core reaches target temperature, pressed compact can be remained on next hour of this temperature or shorter time with abundant realization goal of the invention.
Preferably make the carbon fiber experience surface treatment of production like this, reduce surface energy thus.The vapor-grown carbon fibers that use has a little surface energy can improve greatly to be mediated and the flowability of matrix resin during molded step, makes the shearing rate reduction, thereby can keep conductive network.
Particularly, the preferred 115mJ/m of the surface energy of vapor-grown carbon fibers
2Or it is lower.Use surface energy to surpass 115mJ/m
2Vapor-grown carbon fibers can not allow to reduce the addition of vapor-grown carbon fibers, can not obtain mobile improvement.The preferred 20-115mJ/m of the surface energy of vapor-grown carbon fibers
2, more preferably 30-110mJ/m
2, and then more preferably 40-100mJ/m
2
Adopt reverse-phase chromatography to carry out the measurement of surface energy.This measuring method specifically describes in NipponGomu Kyokaishi the 67th volume o. 11th 752-759 (1994) (THE SOCIETY OFRUBBER INDUSTRY, JAPAN publishes).
Usually, the treatment process of reduction vapor-grown carbon fibers surface energy can be divided into dry method (for example electric discharge or actinic rays method) or wet method (chemical treatment, polymer-coated or the grafting in the presence of catalyzer).Wherein, wait preferred dry method from simplicity, aftertreatment, productivity, environmental problem.
The surface-treated object lesson that is used to reduce surface energy comprises directly to be fluoridized, fluoridizes, adds boron by chemical vapour desposition (CVD) (plasma body, light-or laser) and handle and silanization.
(1) fluoridizes
● directly fluoridize
Fluorine be a kind of be characterised in that its extremely strong electronegativity, its second little size that is only second to hydrogen with and the atom of high reactive behavior.Thereby carbon fiber can directly be fluoridized by enough fluorine gas.In order to control reactive behavior, with rare gas element such as nitrogen or helium fluorine gas is diluted to the concentration of about 0.1-5% usually.Suitable temperature control is also crucial, and reaction is usually in room temperature or more carry out under the low temperature.
● fluoridize by CVD (plasma body, light-or laser)
Chemical vapour desposition (CVD) is meant a kind of deposition process, and wherein the material that exists with gas phase is deposited with solid matter by reaction.To describe herein by fluoridizing that the plasma CVD technology of extensive employing is carried out.
The example of the plasma apparatus that can adopt comprises DC plasma body, low frequency plasma body, high frequency plasma, pulse wave plasma body, three electrode plasmas, microwave plasma, downflow system plasma body and column plasma device.In addition, exploitation recently and simple and easyly cause that air plasma (atmospheric plasma) device of concern is a kind of useful assembly because of operating.
By VGCF is exposed in the plasma body inert atmosphere, and, can realize that the using plasma device is through the fluorizated surface treatment with any treat surface in the following processing gas.
The example that can be used for CVD technology fluorizated processing gas comprises Perfluoroacetone, C
2F
6, C
2F
4, SF
6, CF
4, CF
2Cl
2, CF
3H, NF
3And F/C is than being 1.5 or higher fluorochemical monomer.
Do not have particular restriction for driving source, and can replace plasma body yet with excimer bundle or laser treatment.
(2) adding boron handles
Add the crystallization that boron handle to quicken carbon fiber, thereby reduce the surface energy of carbon fiber and improve the electroconductibility of carbon fiber.For example, this processing can be carried out by this method, promptly will be such as norbide (B when descending processing for 2,000 ℃-3,500 ℃ under the inert atmosphere of preferred one or more argons, helium and neon rare gas
4C), boron oxide (B
2O
3), element state boron, boric acid or boratory boron compound sneak into carbon fiber.
Add boron content in the carbon fiber to and depend on the chemical property and the physical properties and unrestricted of boron compound.For example, using norbide (B
4C) in the situation, in the carbon fiber after pulverizing, this content in the scope of 0.05-10 quality %, preferred 0.1-5 quality %.
When thermal treatment was carried out in the presence of boron compound, the carbon degree of crystallinity in the carbon fiber increased, thereby improved electroconductibility.Boron content is preferably 0.01-5 quality % in the carbon fiber crystal or on the plane of crystal.For the electroconductibility of enhanced carbon fiber and the carbon fiber avidity for resin, more preferably boron content is 0.1 quality % or higher.The boron amount of the carbon atom of the graphene layer of replacement formation simultaneously, (carbon hexagonal network plane) is approximately 3 quality %.Thereby, when boron content is higher than this amount, 5 quality % or higher particularly, excessive boron retains with the form of norbide or boron oxide, and this can reduce electroconductibility, thereby not preferred.
(3) silanization is handled
The example that can be used for the processing gas of silanization in the CVD technology comprises hexamethyldisilane, dimethylamino trimethyl silane and tetramethylsilane.
In order to strengthen the avidity of vapor-grown carbon fibers for matrix polymer, can be with the vapor-grown carbon fibers oxidation, thus phenolic hydroxyl group, carbonyl, quinonyl or lactone group are guided on the surface of carbon fiber.
In addition, vapor-grown carbon fibers can carry out surface treatment with for example coupling agent (titanate/ester group, aluminium base or phosphate/ester base).
Used vapor-grown carbon fibers has the fiber external diameter of 80-500nm among the present invention, preferred 90-250nm, more preferably 100-200nm.When fiber external diameter during less than 80nm, the surface energy of unit volume is index to be increased, and the cohesive force between the fibre debris significantly increases thus.So the accumulative vapor-grown carbon fibers is difficult to be dispensed in the resin by mediating with resin of routine, and fiber aggregate is present in the matrix resin partly, causes having no way of constituting conductive network.Will big shearing force during mediating put on the resin compound when obtaining good carbon fiber dispersion, the accumulative carbon fiber is broken, and the fragment of formation can be dispersed in the resin.Yet cutting off of fiber taken place and ruptured in aggregate when broken, the electroconductibility of the expectation that causes being in no position to take possession of.
Vapor-grown carbon fibers has 40-1,000 length-to-diameter ratio, preferred 50-800, more preferably 60-500, and preferred especially 60-200.
When length-to-diameter ratio (being staple length) increases, fiber yarn tangles together, so the group that forms is difficult to untie, and when length-to-diameter ratio less than 40 the time, thereby mass filler must be sneaked into resin and constitute the conductive network structure, cause resin flow and tensile strength significantly to reduce, and these two kinds of situations are not preferred.
The production of steam carbon fiber has 4-30m
2The BET specific surface area of/g, preferred 8-25m
2/ g, more preferably 10-20m
2/ g.
When the BET specific surface area increased, the surface energy of unit volume increased, and caused carbon fiber to be difficult to be dispersed in the resin and had no way of making the complete coated carbon fiber of resin.As a result, when when the compound that contains this carbon fiber is produced composition, it is bad that electroconductibility and physical strength all become, and this is not preferred.
As resulting by the X-ray diffraction method, spacing d
002Be 0.345nm or littler, preferred 0.343nm or littler, more preferably 0.340nm or littler.As spacing d
002When reducing, the degree of crystallinity of graphite increases, thereby improves the electroconductibility of vapor-grown carbon fibers, and this is preferred.
(Id/Ig) than for 0.1-2, preferred 0.15-1.5, more preferably 0.2-1, wherein Id represents 1,341-1,349cm
-1The peak height of band, Ig represents 1,570-1,578cm
-1The peak height of band is as viewed in Raman (Raman) scattered spectrum.
In order to obtain high conductivity, for the radial and axial all preferred high vapor-grown carbon fibers degree of crystallinity of fiber.Yet, when the fiber external diameter is too small, may can not reduce spacing owing to bending.Thereby the dispersibility of vapor-grown carbon fibers (formation of conductive network) also is a key factor for the formation of giving the required conductive network structure of resin electroconductibility.Thereby in order to regulate this dispersibility, the surface area per unit volume of vapor-grown carbon fibers, length-to-diameter ratio and high-crystallinity all are important parameters, determine fiber external diameter, length-to-diameter ratio, BET specific surface area, as the spacing d by X-ray diffraction method gained
002And the suitable value of (Id/Ig) ratio of determining from raman scattering spectrum.
Do not have particular restriction for polymkeric substance used among the present invention, use mediate with vapor-grown carbon fibers during at 100s
-1Be in the polymkeric substance that melt viscosity is 600Pas or lower state under the shearing rate, be selected from thermosetting resin, light-curable resin and thermoplastic resin particularly.Can use single kind polymkeric substance or be used in combination two or more.
The example of thermosetting resin used in this invention comprises polyethers, polyester, polyimide, polysulfones, Resins, epoxy, unsaturated polyester resin, phenol resins, urethane resin, urea-formaldehyde resin and melamine resin.
The example of thermoplastic resin used in this invention comprises aliphatics or alicyclic polyolefine, as polyethylene, polypropylene, polybutene, polymethylpentene; Aromatic copolycarbonate; Polybutylene terephthalate; Polyethylene terephthalate; Polyphenylene sulfide; Polymeric amide; Polyethers-imide; Polysulfones; Polyethers-sulfone; Polyethers-ether-ketone; Acrylic resin; Styrene resin; Noryl; Non-alkene polyvinyl resin such as liquid crystal polyester.
In these resins, the resin that has alap viscosity during preferably mediating with vapor-grown carbon fibers.Herein, the kneading property under the low viscosity, preferred thermosetting resin.About thermoplastic resin, preferably has the resin of low melting viscosity, as polymeric amide, polyester, liquid crystalline polymers, polyethylene, polypropylene and polystyrene.
Simultaneously, vapor-grown carbon fibers is extremely stable to temperature when mediating, and can at high temperature mediate.Thereby, as long as the negative variation of deterioration, decomposition or any quality does not take place resin, can mediate resin compound at elevated temperatures, thereby reduce the viscosity of resin.
Can produce conductive polymers by comprising the method for mediating each component with conventional equipment such as forcing machine or kneader.The example that is used for the method for molding thermoplastic resin comprises mechanography, extrusion molding, vacuum mold method for making, blow moulding and injection molding process.The example that is used for the method for molded thermoset resin comprises the transfer moulding method.
Putting on the energy that polymkeric substance mixes with vapor-grown carbon fibers in (kneading) is 1,000mJ/m
3Or lower, thereby preferred 50-1,000mJ/m are partly loose in the drawn game of cutting off that prevents vapor-grown carbon fibers
3, more preferably 50-800mJ/m
3, even more preferably 50-500mJ/m
3
Mainly determine mixing energy: the viscosity of composition under given kneading temperature, the rotating speed and the kneading time of kneader of containing polymkeric substance and vapor-grown carbon fibers from following three factors.Thus, kneading is preferably carried out the short period under the low viscosity and the slow speed of revolution.Yet, when being blended in 50mJ/m
3Or during lower carrying out, can not eliminate the variation (shortage homogeneity) of contained vapor-grown carbon fibers concentration in the matrix, thus make the reliability of product feature become bad, and this is not preferred.When mixing energy is 1,000mJ/m
3Or when higher, take place vapor-grown carbon fibers diffusion, cut off drawn game and partly loose, cause obtaining desired characteristics.
At matrix polymer is in the situation of thermosetting polymer, particularly works as at 100s
-1Be in melt viscosity under the shearing rate and be the polymkeric substance of 200Pas state when mixed, preferred mixing energy is 400mJ/m
3Or it is lower.At matrix polymer is in the situation of thermoplastic polymer, particularly works as at 100s
-1Be in melt viscosity under the shearing rate and be the polymkeric substance of 200-600Pas state when mixed, preferred mixing energy is 200-1,000mJ/m
3Or it is lower.
With 1-15 quality %, the amount of preferred 5-10 quality % is sneaked into vapor-grown carbon fibers in the conduction plastic composition of production like this, to obtain 10-10
8The volume specific resistance of Ω cm, preferred 10
2-10
5Ω cm.
When the content of vapor-grown carbon fibers is lower than 1 quality %, the electroconductibility deficiency of gained plastic composition, and when this content surpasses 15 quality %, electroconductibility can be satisfactory, but cause such as the decline of must the raising of cost, plastic properties and extrude or injection-molded during the problem of resin flows being obstructed.
The best mode of foregoing invention
Below will the present invention be described in further detail by embodiment and Comparative Examples.
Embodiment 1-6 and Comparative Examples 1 and 2
＜measuring method 〉
I) fiber external diameter
By in scanning electronic microscope (* 20,000) observes fiber under as 30 width of cloth visual images, (LUZEX-AP, Nireco makes) measures 300 filametntary fiber external diameters with image analyzer, these values on average obtained the mean diameter (external diameter) of vapor-grown carbon fibers.
Ii) length-to-diameter ratio
Average fiber length/fiber diameter with vapor-grown carbon fibers is calculated length-to-diameter ratio.The mean length of vapor-grown carbon fibers is measured 300 filametntary Fibre diameters and is obtained by observing down in scanning electronic microscope (* 2,000) as the fiber of 30 width of cloth visual images and with image analyzer.
Iii) BET specific surface area
The BET specific surface area is measured by nitrogen adsorption method (use NOVA1000, Yuasa Ionics Inc. makes).
Iv) pass through the d that the X-ray diffraction method is measured
200Value
As internal standard substance, measure d with Si by powder x-ray diffraction (using Rigaku Geigerflex)
200Value.
V) measure (Id/Ig) ratio from raman scattering spectrum
Measure (Id/Ig) ratio with Raman spectrometer (LabRam HR, Jobin Yvon make), wherein the Id representative as raman scattering spectrum survey 1,341-1,349cm
-1The peak height of band, Ig represents 1,570-1,578cm
-1The peak height of band.
The method of the manufacturing vapor-grown carbon fibers A that adopts among the embodiment and the characteristic of carbon fiber A below will be described.At first, by benzene, ferrocene and sulphur being mixed to come preparation raw material liquid with ratio (quality) 91: 7: 2.With this stock liquid with supply with as the hydrogen of carrier gas the Reaktionsofen that is heated to 1,200 ℃ (internal diameter: 100mm, highly: 2,500mm) and spraying.The input speed of raw material and hydrogen stream is adjusted into 10g/min and 60L/min respectively.Will by the reaction product (150g) that above method obtains pack into plumbago crucible (internal diameter: 100mm, highly: 10mm), under argon gas in 1,000 ℃ was cured one hour, subsequently under argon gas in 2,800 ℃ of greyings one hour, produce vapor-grown carbon fibers A thus.
Find that this vapor-grown carbon fibers A has fiber diameter 150nm, average fiber length 9.0 μ m, length-to-diameter ratio 60, BET specific surface area 13m
2/ g, d
2000.339nm and Id/Ig 0.2.
The method of the manufacturing vapor-grown carbon fibers B that adopts among the embodiment and the characteristic of carbon fiber B below will be described.At first, by benzene, ferrocene and sulphur being mixed to come preparation raw material liquid with ratio (quality) 97: 2: 1.With this stock liquid with supply with as the hydrogen of carrier gas the Reaktionsofen that is heated to 1,200 ℃ (internal diameter: 100mm, highly: 2,500mm) and spraying.The input speed of raw material and hydrogen stream is adjusted into 5g/min and 90L/min respectively.
Will by the reaction product (150g) that above method obtains pack into plumbago crucible (internal diameter: 100mm, highly: 150mm), under argon gas in 1,000 ℃ was cured one hour, subsequently under argon gas in 2,800 ℃ of greyings one hour, produce vapor-grown carbon fibers B thus.
Find that this vapor-grown carbon fibers B has fiber diameter 80nm, average fiber length 12.0 μ m, length-to-diameter ratio 150, BET specific surface area 25m
2/ g, d
2000.340nm and Id/Ig 0.14.
The method of the manufacturing vapor-grown carbon fibers C that adopts among the embodiment and the characteristic of carbon fiber C below will be described.At first, by benzene, ferrocene and sulphur being mixed to come preparation raw material liquid with ratio (quality) 92: 6: 2.With 300 ℃ of vaporizers this stock liquid is heated and evaporation.With the unstripped gas of so preparation with supply with as the hydrogen of carrier gas the Reaktionsofen that is heated to 1,200 ℃ (internal diameter: 100mm, highly: 2,500mm).The input speed of raw material and hydrogen stream is adjusted into 8g/min and 60L/min respectively.Will be by the reaction product (150g) that above method the obtains plumbago crucible (internal diameter: 100mm of packing into, highly: 150mm), under argon gas in 1,000 ℃ was cured one hour, subsequently under argon gas in 2,800 ℃ of greyings one hour are produced vapor-grown carbon fibers C (below be sometimes referred to as " VGCF-S ") thus.
Find that this vapor-grown carbon fibers C (VGCF-C) has fiber diameter 100nm, average fiber length 13.0 μ m, length-to-diameter ratio 130, BET specific surface area 20m
2/ g, d
2000.340nm and Id/Ig 0.14.
Estimate the method for polymkeric substance
For every kind of resin combination 10
8Ω cm or lower volume specific resistance are measured by four-probe method (with Loresta HP MCP-T410, Mitsubishi Chemical Industries, Ltd. produces); For 10
8Ω cm or higher volume specific resistance use insulation resistance test device (ultra-high resistance/microgalvanometer R8340, ADVANTEST makes) to measure.
Under argon gas, every kind of moulded product of conductive polymers was lighted (heating) 30 minutes in 1,000 ℃, collect vapor-grown carbon fibers thus.Under scanning electronic microscope, observe the vapor-grown carbon fibers of so collecting, obtain average fiber length, estimate the degree of the fiber cutting that rises because of kneading thus by image analysis.
Measure the viscosity (flowability) of matrix polymer and composition with Capirograph (a kind of capillary type rheometer).
Embodiment 1
With Laboplast mill R100 (Toyo Seiki Seisakusho, Ltd. product) with polyvinyl resin (Sun-Allomer PWB02N (MFI:70), the product of SunAllomer Ltd.) (90 quality %) and vapor-grown carbon fibers A (10 quality %) under 200 ℃ and 40rpm melt kneading 5 minutes (mediate can: 200mJ/m
3).Should mediate product in 200 ℃ and 200kgf/cm with 50-ton hot molding device (Nippo Engineering manufacturing)
2Lower mould 30 seconds is produced the t plate sample of 10mm * 10mm * 2mm thus.This matrix resin in 200 ℃ at 100s
-1Shearing rate under have the melt viscosity of 100Pas.
Embodiment 2
With Laboplast mill R100 (Toyo Seiki Seisakusho, Ltd. product) with polyamide 6 resin (Novamid1010, Mitsubishi Chemical Industries, the product of Ltd.) (90 quality %) and vapor-grown carbon fibers A (10 quality %) under 260 ℃ and 40rpm melt kneading 10 minutes (mediate can: 500mJ/m
3).Should mediate product in 200 ℃ and 200kgf/cm with 50-ton hot molding device (product of Nippo Engineering)
2Lower mould 30 seconds is produced the t plate sample of 10mm * 10mm * 2mm thus.This matrix resin in 260 ℃ at 100s
-1Shearing rate under have the melt viscosity of 80Pas.
Embodiment 3
With Laboplast mill R100 (Toyo Seiki Seisakusho, Ltd. make) with acrylic resin (Sun-Allomer PWB02N (MFI:70), the product of SunAllomer Ltd.) (54 quality %), polyvinyl resin (J-Rex HD KMA90K (MFI:30), Japan PolyolefinsCo., the product of Ltd.) (46 quality %) and vapor-grown carbon fibers A (10 quality %) under 180 ℃ and 40rpm melt kneading 5 minutes (mediate can: 180mJ/m
3).Should mediate product in 200 ℃ and 200kgf/cm with 50-ton hot molding device (product of Nippo Engineering)
2Lower mould 30 seconds is produced the t plate sample of 10mm * 10mm * 2mm thus.This matrix resin in 180 ℃ at 100s
-1Shearing rate under have the melt viscosity of 150Pas.
Embodiment 4
With Laboplast mill R100 (Toyo Seiki Seisakusho, Ltd. make) with acrylic resin (Sun-Allomer PWB02N (MFI:70), the product of SunAllomer Ltd.) (95 quality %) and vapor-grown carbon fibers B (5 quality %) under 200 ℃ and 40rpm melt kneading 5 minutes (mediate can: 150mJ/m
3).Should mediate product in 200 ℃ and 200kgf/cm with 50-ton hot molding device (product of Nippo Engineering)
2Lower mould 30 seconds is produced the t plate sample of 10mm * 10mm * 2mm thus.This matrix resin in 200 ℃ at 100s
-1Shearing rate under have the melt viscosity of 100Pas.
Embodiment 5
With Laboplast mill R100 (Toyo Seiki Seisakusho, Ltd. product) with Resins, epoxy (EPICLON HP-7200, Dainippon Ink and Chemicals, the product of Inc.) (90 quality %) and vapor-grown carbon fibers A (10 quality %) under 80 ℃ and 40rpm melt kneading 5 minutes (mediate can: 100mJ/m
3).Week 50-ton hot molding device (product of Nippo Engineering) should be mediated product in 175 ℃ and 100kgf/cm
2Lower mould 5 hours is produced the t model of 10mm * 10mm * 2mm thus.This matrix resin in 80 ℃ at 100s
-1Shearing rate under have the melt viscosity of 30Pas.
Embodiment 6
With Laboplast mill R100 (Toyo Seiki Seisakusho, Ltd. product) with acrylic resin (Sun-Allomer PWB02N, the product of SunAllomer Ltd.) (95 quality %) and vapor-grown carbon fibers C (5 quality %) under 200 ℃ and 40rpm melt kneading 5 minutes (mediate can: 150mJ/m
3).Should mediate product in 200 ℃ and 200kgf/cm with 50-ton hot molding device (product of Nippo Engineering)
2Lower mould 30 seconds is produced the t plate sample of 10mm * 10mm * 2mm thus.This matrix resin in 200 ℃ at 100s
-1Shearing rate under have the melt viscosity of 100Pas.
The comparative example 1
With Laboplast mill R100 (Toyo Seiki Seisakusho, Ltd. make) with acrylic resin (Sun-Allomer PWB02N (MFI:70), the product of SunAllomer Ltd.) (90 quality %) and vapor-grown carbon fibers A (10 quality %) under 180 ℃ and 40rpm melt kneading 20 minutes (mediate can: 1,100mJ/m
3).Should mediate product in 200 ℃ and 200kgf/cm with 50-ton hot molding device (product of Nippo Engineering)
2Lower mould 30 seconds is produced the t plate sample of 10mm * 10mm * 2mm thus.This matrix resin in 180 ℃ at 100s
-1Shearing rate under have the melt viscosity of 150Pas.
The comparative example 2
With Laboplast mill R100 (Toyo Seiki Seisakusho, Ltd. make) with acrylic resin (Sun-Allomer PWB02N (MFI:70), the product of SunAllomer Ltd.) (90 quality %) and vapor-grown carbon fibers A (10 quality %) under 170 ℃ and 80rpm melt kneading 20 minutes (mediate can: 3,000mJ/m
3).Should mediate product in 200 ℃ and 200kgf/cm with 50-ton hot molding device (product of Nippo Engineering)
2Lower mould 30 seconds is produced the t plate sample of 10mm * 10mm * 2mm thus.This matrix resin in 170 ℃ at 100s
-1Shearing rate under have the melt viscosity of 180Pas.
The results are shown in the table 1 of the result of embodiment 1-6 and comparative example 1 and 2.
Table 1
| Material resin | Mediating can (mJ/m 3) | The VGCF type | Content quality % | Volume specific resistance (Ω cm) | The mean length of collected fiber (μ m) | |
| Embodiment 1 | PP ＊1 | 200 | A | 10 | 9.5×10 2 | 8.8 |
| Embodiment 2 | PA6 ＊2 | 500 | A | 10 | 3.9×10 5 | 8.5 |
| Embodiment 3 | PP/PE ＊3 | 180 | A | 10 | 1.0×10 2 | 8.8 |
| Embodiment 4 | PP | 150 | B | 5 | 1.1×10 2 | 11.8 |
| Embodiment 5 | Epoxy ＊4 | 100 | A | 10 | 8.4×10 2 | 8.7 |
| Embodiment 6 | PP | 150 | C | 5 | 2.0×10 2 | 12.5 |
| The comparative example 1 | PP | 1,100 | A | 10 | 1.5×1010 | 7.3 |
| The comparative example 2 | PP | 3,000 | A | 10 | 4.2×10 15 | 6.5 |
* 1: polypropylene (Sun-Allomer PB02N, the product of SunAllomer Ltd.)
* 2: polyamide 6 (Novamid1010, Mitsubishi Chemical Industries, the product of Ltd.)
* 3: the mixture of polypropylene (Sun-Allomer PB02N, the product of SunAHomer Ltd.) (54 quality %), polyethylene (J-Rex HDKMA90K, Japan Polyolefins Co., the product of Ltd.) (46 quality %)
* 4: Resins, epoxy (EPICLON HP-7200, Dainippon Ink and Chemicals, the product of Inc.)
Embodiment 7-14 and comparative example 3-8
VGCF
As vapor-grown carbon fibers, and use VGCF (registered trademark) (product of Showa Denko K.K., fiber diameter: 150nm, average fiber length: 9 μ m, length-to-diameter ratio: 60, BET specific surface area: 13m
2/ g, d
200=0.339nm and Id/Ig=0.2).Same VGCF also is used for surface treatment.
VGCF-S
As vapor-grown carbon fibers, and use VGCF-S (fiber diameter: 100nm, average fiber length: 13 μ m, length-to-diameter ratio: 130, BET specific surface area: 20m
2/ g, d
200=0.340nm and Id/Ig=0.14).Same VGCF-S also is used for surface treatment.
Surface treatment method
(1) fluoridation
Using plasma powder treatment equipment (product of Samco International Kenkyusho)
In will generating the sample flask of plasma body, with argon gas that serves as carrier gas and the CF that serves as reactant gases
4Carbon fiber with vapor-grown places, and gaseous tension is adjusted to 1 holder.High frequency electric source with frequency 13.54MHz carries out surface treatment to vapor-grown carbon fibers with the discharge of 60 seconds 200W in this flask.
(2) adding boron handles
With B
4C powder (median size: 15 μ m) (120g) be added in the vapor-grown carbon fibers (2.88kg), use the Henschel mixing tank with the mixture thorough mixing.Pack in the tubular plumbago crucible (volume 50L) this mixture and extruding, thus tap density is adjusted to 0.07g/cm
3In with graphite compressing tablet extruding pressed compact with lid with crucible cover on and move in the Acheson type stove and heat-treat.Thermal treatment temp is 2,900 ℃, carries out this processing 60 minutes under this temperature.After finishing thermal treatment and subsequent cooling, treated vapor-grown carbon fibers is shifted out crucible and broken with the Bantam abrasive dust.Remove non-fibrous material with air classifier.Remain unchanged through the Fibre diameter of handling the fiber that so obtains.
(3) (silanization processing)
Using plasma powder treatment equipment (product of Samco International Kenkyusho).
In the sample flask, place with argon gas that serves as carrier gas and the carbon fiber of the tetramethylsilane that serves as reactant gases, and gaseous tension is adjusted to 1 holder with vapor-grown.High frequency electric source with frequency 13.54MHz carries out surface treatment (air pressure: 1 holder) to vapor-grown carbon fibers with the discharge of 60 seconds 200W in this flask.
Surface energy is measured
Carry out the measurement of surface energy with reverse-phase chromatography, this method such as THE SOCIETY OFRUBBER INDUSTRY are described in Nippon Gomu Kyokaishi the 67th volume o. 11th 752-759 (1994) that JAPAN publishes.According to this method, no matter specimen shape how can both be with simple relatively method surface measurements free energy (surface tension), and can obtain the pinpoint accuracy of measurement.Particularly, the following measurement.
To serve as the vapor-grown carbon fibers that absorbs phase pack into separately glass column (internal diameter: 3mm, length: 2.1m).(detector: TCD) (product of Shimadzu Corporation) is that carrier gas is measured under 90 ℃ of column temperatures with the helium with gas chromatograph GC-7A.In order to estimate dispersing property, normal alkane pentane, hexane and heptane are used as sample separately.For evaluation polarity, benzene and tetrahydrofuran (THF) are used as alkali lye for every kind, and methylene dichloride and chloroform are used as acid solution separately.
The measuring result of the surface energy values of table 2 expression vapor-grown carbon fibers and surface treated vapor-grown carbon fibers.
Table 2
| Carbon fiber type | Surface energy (mJ/m 2) |
| VGCF | 119 |
| The VGCF that boron is handled | 98 |
| The VGCF of fluoridation | 85 |
| The VGCF that silanization is handled | 90 |
| VGCF-S | 120 |
| The VGCF-S of fluoridation | 84 |
The kneading method
(volume: 100mL) (product of Toyo Seiki) is as kneader with the Laboplast mill.
Usually, the Laboplast mill is used for estimating polymkeric substance such as thermoplastic resin, thermosetting resin or elastomeric processing characteristics based on combined experiments.
Be equipped with two in the sample kneading portion of the mixing tank of this process heating and mediate blades and resin temperature detector, described blade can be with different directions from each other with different rotational speed.
Supply with the resin of this mixing tank and mediate, and depend on that the fusion of resin and the dispersion of filler take place the characteristic of resin and filler when mediating by shearing.Fusion and dispersive feature can be used as the moment of torsion that puts on the blade and are detected.When use has the resin of high melt viscosity, quite high moment of torsion, promptly shearing force puts on the mixture, thus uniform filling is disperseed.
Method of moulding
I) thermoplastic resin
Under the cylinder temperature that is shown in Table 2, every kind of thermoplastic resin is molded as sheet material (100 * 100 * 2mm) with injection molding machine (Sicap, 75 tons of locking forces, the product of Sumitomo Heavy Industries Ltd.).PP, PA6 and PPS are respectively in the molding temperature lower mould of 20 ℃, 40 ℃ and 120 ℃.
Ii) thermosetting resin
With moulding press (M-70C-TS, Meiki Co., the product of Ltd.) thermosetting resin is molded as sheet material (100 * 100 * 2mm).Allyl ester is in the mould temperature lower mould of gentle 160 ℃ of 80 ℃ tube, retention time 10 minutes.
Used resin
I) thermoplastic resin
Polypropylene (PP), the product of SunAllomer Ltd.
PM 900A (MI＝30)
PW 201N (MI＝0.6)
Polyamide 6 (PA6), Toray Industries, the product of Inc.
Amilan CM1007
Polyphenylene sulfide (PPS), the product of Toso Corporation
Susteel F11
Ii) thermosetting resin
The allyl ester resin, the product of Showa Denko K.K.
AA 101 (viscosity: 630,000cps (30 ℃)), used organo-peroxide: dicumyl peroxide (Percumyl D, Nippon Oil ﹠amp; Fats Co., the product of Ltd.).
The melt viscosity value of used resin (under the shearing rate of 100s-1) is shown in Table 3.
Table 3
The evaluation of physical properties
The measurement of physical properties
Measure volume specific resistance according to four-probe method (JIS K7194).
According to 3 mixture strength methods (sample: 100 * 10 * 2mm, spacing: 64mm, mixing velocity: the 2mm/min) mixed nature of assess sample.
The measurement of viscosity (Capirograph)
Capirograph is a kind of capillary type mobilometer, is used for the measurement as JIS K7119 defined.By adopting this mobilometer, measure the flowability of every kind of matrix polymer and every kind of composition.Table 3 shows the measurement structure about matrix polymer, and table 4 and 5 shows the result about resin combination.
Show the result of embodiment and comparative example's result in the table 4 and 5 respectively.
The result of table 4: embodiment
| Embodiment | Resin grade molding temperature | Carbon fiber type | Amount of carbon fiber (quality %) | Volume specific resistance (Ω cm) | Melt viscosity (Pas) | Mixture strength (Mpa) |
| Embodiment 7 | PP PM 900A 220℃ | The VGCF that adds boron | 5 | 3×10 0 | 200 | 55 |
| Embodiment 8 | PP PM 900A 220℃ | Fluorizated VGCF | 5 | 4×10 0 | 180 | 52 |
| Embodiment 9 | PP PM 900A 220℃ | The VGCF of silanization | 5 | 1×10 1 | 190 | 50 |
| Embodiment 10 | PP PW 201N 280℃ | The VGCF that adds boron | 5 | 5×10 2 | 550 | 50 |
| Embodiment 11 | PA6 CM 1007 240℃ | Fluorizated VGCF | 10 | 2×10 2 | 200 | 120 |
| Embodiment 12 | PPS F11 320℃ | The VGCF that adds boron | 10 | 1×10 0 | 300 | 75 |
| Embodiment 13 | 60 ℃ of allyl ester AA101 | The VGCF of silanization | 5 | 2×10 2 | 150 | 80 |
| Embodiment 14 | PP PM 900A 220℃ | Fluorizated VGCF-S | 2 | 3×10 1 | 180 | 50 |
Table 5: comparative example's result
| Embodiment | Resin grade molding temperature | Carbon fiber type | Amount of carbon fiber (quality %) | Volume specific resistance (Ω cm) | Melt viscosity (Pas) | Mixture strength (MPa) |
| The comparative example 3 | PP PM 900A 220℃ | VGCF | 3 | 3×10 10 | 250 | 50 |
| The comparative example 4 | PP PW 201N 220℃ | The VGCF that adds B | 10 | 5×10 15 | 1,100 | 50 |
| The comparative example 5 | PA6 CM 1007 240℃ | VGCF | 10 | 1×10 12 | 300 | 100 |
| The comparative example 6 | PPS F11 320℃ | VGCF | 10 | 5×10 8 | 400 | 60 |
| The comparative example 7 | 101 60 ℃ of allyl ester AA | VGCF | 5 | 3×10 12 | 200 | 70 |
| The comparative example 8 | PP PW 201N 220℃ | VGCF-S | 2 | 3×10 4 | 1100 | 45 |
The threshold value of the table 6 various vapor-grown carbon fibers of expression under different molding temperatures.
When the matrix material that contains polypropylene (PM 900A) and VGCF during, find that threshold value is 7% 220 ℃ of lower mould.In other words, when reaching 7%, the addition of VGCF obtains high electroconductibility (formation conductive network).When the modification VGCF that uses surface energy to reduce (add boron, fluorizated or silanization), this threshold value drops to 3%, shows effect of the present invention.
When the matrix material that contains polypropylene (PW 210N) and add boron VGCF during 220 ℃ of lower mould, conductive network is broken because of high melt viscosity, thus threshold value is increased to 15%.Yet when the rising molding temperature, because melt viscosity reduces, this threshold value can drop to 4%.
When the matrix material that contains polyamide 6 and VGCF during, find that this threshold value is 13% 240 ℃ of lower mould.Yet when using when fluoridizing VGCF, this threshold value reduces to 8%, shows the effect of the surface energy that has reduced.
When the matrix material that contains polyphenylene sulfide and VGCF during, find that this threshold value is 10% 320 ℃ of lower mould.Yet when use added the VGCF of boron, this threshold value reduced to 7%.
Contain in the situation of thermoset allyl ester and VGCF at matrix material, find that this threshold value is 8%.Yet when using the VGCF of silanization, this threshold value reduces to 3%, shows the effect of surface energy reduction to VGCF.
When the matrix material that contains polypropylene (PW 210N) and VGCF-S during, find that this threshold value is 3% 220 ℃ of lower mould.Yet, when use have reduction surface energy fluoridize VGCF-S the time, this threshold value reduces to 1.5%, this shows that to use this fluorizated VGCF-S effective.
Table 6: the threshold value of the type of vapor-grown carbon fibers, molding temperature and resin
| Carbon fiber type | Resin, grade | Molding temperature | Threshold value |
| VGCF | PP，PM 900A | 220℃ | 7％ |
| The VGCF that adds B | PP，PM 900A | 220℃ | 3％ |
| Fluorizated VGCF | PP，PM 900A | 220℃ | 3％ |
| The VGCF of silanization | PP，PM 900A | 220℃ | 3％ |
| The VGCF that adds B | PP，PW 201N | 220℃ | 15％ |
| The VGCF that adds B | PP，PW 201N | 280℃ | 4％ |
| VGCF | PA6，CM 1007 | 240℃ | 13％ |
| Fluorizated VGCF | PA6，CM 1007 | 240℃ | 8％ |
| VGCF | PPS，F11 | 320℃ | 10％ |
| The VGCF that adds B | PPS，F11 | 320℃ | 7％ |
| VGCF | Allyl ester, AA101 | 60℃ | 8％ |
| The VGCF of silanization | Allyl ester, AA101 | 60℃ | 3％ |
| VGCF-S | PP，PW 201N | 220℃ | 3％ |
| VGCF | PP，PW 201N | 220℃ | 1.5％ |
Industrial applicibility
Conducting polymer of the present invention will have excellent business efficiency and the vapor-grown carbon fibers that can provide in batches as the conduction excipient. In this conducting polymer, kneading when mediating matrix polymer and vapor-grown carbon fibers by control can also form and keep the conductive network structure thus, can reduce the cut-out of vapor-grown carbon fibers, as a result, can show excellent electric conductivity by a small amount of vapor-grown carbon fibers being sneaked into the polymer that obtains. Thereby polymer keeps its intrinsic flowability and splendid mechanograph is provided. In addition, because vapor-grown carbon fibers only with a small amount of interpolation, so the reduction of mechanical strength can be reduced to floor level, provides the product with height reliability thus.
Conducting polymer of the present invention has splendid electrical property, such as electric conductivity and antistatic behaviour, but have in addition splendid surface flatness, size accuracy, glossiness, mechanical strength coating, heat endurance and resistance to impact, can be used in many industrial circles, for example be used for phoresying or coat the material of electronic building brick the field, be used for office automation (OA) device and electronic installation assembly the field and for the field of the antistatic coating material of automobile.
Claims (11)
1. a method of producing conductive polymers is included in 1,000mJ/m
3Or under the lower mixing energy, will be at 100s
-1Be in melt viscosity under the shearing rate and be the step of the vapor-grown carbon fibers blend of the polymkeric substance of 600Pas or lower state and 1-15 quality %,
Described vapor-grown carbon fibers has 115mJ/m
2Or lower surface energy, the fiber external diameter of 80-500nm, 40-1,000 length-to-diameter ratio, 4-30m
2The BET specific surface area of/g,
And add the processing of boron processing, wet method or dry method silanization with the reduction surface energy through wet method or dry fluorination process processing, wet method or dry method,
Described polymkeric substance be selected from following at least a: as the polyethers of thermosetting polymer, polyester as thermosetting polymer, polyimide as thermosetting polymer, polysulfones as thermosetting polymer, Resins, epoxy as thermosetting polymer, unsaturated polyester resin as thermosetting polymer, phenol resins, urethane resin as thermosetting polymer, urea-formaldehyde resin as thermosetting polymer, melamine resin as thermosetting polymer, polymeric amide as thermoplastic polymer, polyester as thermoplastic polymer, liquid crystalline polymers as thermoplastic polymer, polyethylene as thermoplastic polymer, polypropylene as thermoplastic polymer, as the polyphenylene sulfide of thermoplastic polymer with as the polystyrene of thermoplastic polymer.
2. the method for the production conductive polymers described in claim 1, wherein polymkeric substance is at 100s
-1Be in melt viscosity under the shearing rate and be the uncured thermosetting polymer of 200Pas or lower state, and blend is at 400mJ/m
3Or carry out under the lower mixing energy.
3. the method for the production conductive polymers described in claim 1, wherein polymkeric substance is at 100s
-1Be in the thermoplastic polymer that melt viscosity is the state of 200-600Pas under the shearing rate, and blend is at 200-1,000mJ/m
3Mixing energy under carry out.
4. as the method for each described production conductive polymers among the claim 1-3, the wherein 0.345nm that obtains by the X-ray diffraction method of vapor-grown carbon fibers tool or littler d
002, 0.1-2 the Id/Ig ratio, wherein Id represents 1,341-1,349cm
-1The peak height of band, Ig represents 1,570-1,578cm
-1The peak height of band, these bands are observed in raman scattering spectrum.
5. the method for production conductive polymers as claimed in claim 1, wherein vapor-grown carbon fibers has passed through in inert atmosphere 2,000-3,500 ℃ thermal treatment.
6. conductive polymers is by being obtained by each described production method among the claim 1-5.
7. moulded product, the conductive polymers that is obtained by each described production method among the claim 1-5 constitutes.
8. an outside appurtenances that is used for automobile uses the conductive polymers that is obtained by each described production method among the claim 1-5.
9. an electromagnetic shielding material uses the conductive polymers that is obtained by each described production method among the claim 1-5.
10. an antistatic material adopts the conductive polymers that is obtained by each described production method among the claim 1-5.
11. a conductive adhesion material uses the conductive polymers that is obtained by each described production method among the claim 1-5.
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