CN100587009C - Resin composition for GHz-band electronic component and GHz-band electronic component - Google Patents

Abstract

Disclosed is a resin composition for GHz-band electronic components which contains at least one resin selected from the group consisting of thermoplastic resins, curing resins and composite resins ofa thermoplastic resin and a curing resin, and a nanoscale carbon tube. The nanoscale carbon tube is contained in the resin composition in an amount of 0.0001-0.4 weight% relative to the resin contained in the composition. Also disclosed is an electronic component produced from such a resin composition.

Description

The charged sub-element of GHz is with resin combination and the charged sub-element of GHz

Technical field

The present invention relates to the charged sub-element resin combination of GHz.Know clearly it, the present invention relates to possess low dielectric loss angle tangent and be suitable for making circuit board material, particularly GHz electric, electronics be with the circuit board material of usefulness and the resin combination of other electronic component.In addition, the invention still further relates to the electronic component that obtains by this resin combination.

Background technology

In recent years,, expect very much miniaturization, lightweight, the high speed of information communication devices such as PHS, portable phone, seek the electrically insulating material of corresponding low-k with it along with the rapid increase of communication information amount.Particularly the frequency band of the radiowave of using in the mobile communication equipments such as portable mobile communicating such as car phone, digital mobile phone, satellite communications etc. uses the high frequency band of band from MHz to GHz.In addition, because the high frequency band that is called as microwave milli wavestrip is used in the minimizing of spendable wavelength band more and more.In addition, the CPU frequency of computer has also reached GHz band level, and high frequencyization is just in fast development.For the miniaturization that realizes the signal equipment that high frequency band therewith adapts, lightweight, must develop and have the good high frequency transmission characteristic and the electrically insulating material of low dielectric characteristics concurrently.

Physical propertys such as under many situations, the circuit board material of electronics requires that dielectric characteristicies such as specific inductivity and dielectric loss angle tangent are low, thermotolerance and physical strength are good.So-called specific inductivity (∈) is the parameter of the degree of polarization in the expression dielectric medium, and specific inductivity is high more, and the propagation delay of electrical signal is big more.Therefore, in order to improve the velocity of propagation of signal, can carry out high-speed computation, preferred specific inductivity is low.Dielectric loss angle tangent (tan δ) is the parameter of the conversion of signals propagated in the expression dielectric medium loss of signal amount when becoming hot, and dielectric loss angle tangent is low more, and the loss of signal is few more, and the signal transport is just high more.

That is, be called the energy waste in the transmittance process of dielectric loss in the element circuitry, but since this energy waste emit in element circuitry as heat energy, so not preferred.This energy waste is to produce owing to the dipole that produces by dielectric polarization vibrates because of electric field change in low-frequency band, produces by ionic polarization and electronic polarization in high frequency band.The ratio of energy stored is called dielectric loss angle tangent in energy that 1 alternating-electric field was consumed in the dielectric medium in the cycle and the dielectric medium, represents with tan δ.

Owing to tan δ increase along with frequency in high frequency band increases, and cause the thermal value of per unit area to increase, therefore,, must use the little material of tan δ for the dielectric loss that makes insulating material is as much as possible little by the High Density Packaging of electronic component.By the little low medium electrical property high polymer material of working medium loss, suppress the heating that dielectric loss and resistance cause, its result, the flase operation of signal also tails off, and therefore, in the high frequency communications field, expects very much the few material of signal transmission loss (energy waste).

As material, thermosetting resins such as thermoplastic resins such as polyolefine, vinyl chloride resin, fluoro-resin, unsaturated polyester resin, polyimide resin, Resins, epoxy, bismaleimide-triazine resin (BT resin), crosslinkable polyphenylene oxide, curable polyphenylene oxide etc. have been developed usually in order to satisfy following characteristic with electrical characteristic such as electrical insulating property, low-ks.

The boring processibility of veneer sheet, machinability

High heat resistance

The low linear expansion rate

Adaptation or tackiness (Copper Foil adaptation) with metal conductor layer

Physical strength

Film forms ability power

Can in wider scope, set specific inductivity arbitrarily

Insulativity

Weathering resistance

Dielectric characteristics is little to the dependency of temperature, humidity.

But there is problem as described below in above-mentioned resin.

(1) polyolefine

Because polyolefine such as polyethylene, polypropylene have covalent linkage such as C-C key, and do not have big polar group, therefore, its electrical characteristic, particularly insulated electro are resistive good, but have the low shortcoming of thermotolerance.Electrical characteristic (dielectric loss, specific inductivity etc.) when therefore at high temperature using worsen, and are not suitable as the insulating film (layer) of electrical condenser etc.

Polyethylene and polypropylene be as membranaceous formation, and use binding agent lining to be bonded on the electro-conductive material it, but this method complete processing complexity not only, and the problem that exists linings such as being difficult to make the cambial thickness attenuation of film to form.

(2) vinyl chloride resin

The resistive height of the insulated electro of vinyl chloride resin, chemical-resistant, flame retardant resistance are good, but and polyolefine be short of thermotolerance equally, have the big shortcoming of dielectric loss.

(3) pvdf resin, trifluoro-ethylene resin and perfluoro-ethylene resin

These polymkeric substance that contain fluorine atom in the molecular chain, electrical characteristic (low-k, low dielectric loss), thermotolerance, chemical stability are good, but obtaining being shaped and shortcoming is being arranged aspect the shaping processability of classes such as thing or film, the formation ability of filming by heat-treat processing as thermoplastic resin, when making device by this resin, cost is quite high.And, there is the restricted shortcoming of Application Areas because the transparency is low.

(4) Resins, epoxy

The performance that Resins, epoxy is resistive in insulated electro, meet the demands aspect insulation breakdown intensity and the heat resisting temperature.But its permittivity ratio is higher to be more than 3, can not obtain satisfied characteristic.And exist film to form the shortcoming of scarce capacity.Known polyphenylene oxide resin (PPO) and multifunctional cyanate ester resene, further in these resins, add other resin, add radical polymerization initiator, make it carry out the formed curable MODIFIED PP O resin combination of preparatory response, but its low-kization is not able to the level that fully satisfies.And, in order to improve the insufficient Resins, epoxy of thermotolerance, also studying for example combination of phenol linear phenolic resin, vinyl cyanate resin etc., but also having the significantly shortcoming of decline of mechanical characteristic as film.Therefore, in order to keep the above-mentioned problem of improvement on the basis of electrical characteristic, specifically, for improve its hot workability and with the adaptation and the cohesiveness of metallic conductors (layer) such as copper, branching ring-type amorphous fluoropolymer, perfluoro-ethylene monomer and other monomeric multipolymer etc. have been proposed, though electrical characteristic such as its specific inductivity, dielectric loss can satisfy, but because the influence of the methene chain that exists in the high polymer main chain makes its thermotolerance deterioration, so do not obtain yet to good materials of adaptation such as electronics substrates.

(5) polyimide, polyethersulfone, polyphenylene sulfide, polysulfones, thermosetting polyphenylene ether (PPE), polyethylene terephthalate

As the resistive good advanced low-k materials of dielectricity, insulated electro the performance that further requires, owing in the process of making device, must have welding sequence, therefore, at least require it can bear 120 seconds thermotolerance of heating in the time of 260 ℃, and must be chemical stability and wet fastness and all good materials of mechanical characteristics such as thermotolerance, alkali resistance.As everyone knows, the macromolecular material that satisfies these requirements for example has: polyimide, polyethersulfone, polyphenylene sulfide, polysulfones, thermosetting polyphenylene ether (PPE), polyethylene terephthalate etc.But even these resins, its dielectric loss also can increase in the GHz band.

Realize foregoing characteristic in view of independent use resin and have all difficulties, therefore, proposed in resin, to add additive, to improve the electrical properties of resin.For example, open in flat 8-134263 number the spy, proposed: when in synthetic resins, mixing the specific metal silicate fibre-like thing of specified quantitative, specific inductivity and dielectric loss angle tangent can not risen to the degree that obstruction is used in high frequency band, also can improve heat conductivity, thermotolerance and physical strength, and, according to the resin kind of adding, under the situation of the specific inductivity of keeping same degree, dielectric loss angle tangent is significantly descended, therefore, can be highly suitable for as with synthetic resins in the past be suitable for electric, electronic component has the circuit board material of different electric purposes, high frequency circuit board material particularly.

More specifically, open the spy and to have proposed a kind of high-frequency electronic element resin combination in flat 8-134263 number, it is characterized in that, in thermoplastic resin (except the polyamide resin) and/or thermosetting resin (except the resol), will be with general formula aMxOybSiO ₂CH ₂(at this, a, b and c represent arithmetic number to O.X is that 1 o'clock y represents 1, and x is that 2 o'clock y represent 1 or 3.M represents to be selected from the metallic element more than at least a kind in the group that is made of Mg, Cr, Mn, Fe, Co, Ni, Cu, Zn, Al, Ga, Sr, Y, Zr, Nb, Mo, Pb, Ba, W and Li.) the metal silicate fibre-like material of expression is the fortifying fibre of main component, is that the ratio of benchmark 5～60 weight % is added with the gross weight of above-mentioned resin and above-mentioned fibrous material.

But, to open in the flat 8-134263 communique above-mentioned spy, fortifying fibre is at least more than about 5 weight % with respect to the cooperation ratio of thermoplastic resin or thermosetting resin, and must use this fortifying fibre in a large number.

Summary of the invention

Main purpose of the present invention is that the additive that just can reduce the dielectric loss (or tan δ) in the GHz band is on a small quantity added in exploitation in resin, the electronic component resin combination that can satisfy various requirement neatly is provided.

In addition, other purpose of the present invention is, provide be highly suitable for making have low-k, circuit board material, the particularly circuit board material of GHz band usefulness that the Electrical and Electronic equipment of low dielectric loss angle tangent, high heat resistance, high mechanical strength is used and the resin combination of other electronic component.

To achieve these goals, the present inventor studies without single devotion, found that, in synthetic resins during with a small amount of interpolation nano-scale carbon tube in the specialized range (Na ノ ス ケ one Le カ one ボ Application チ ユ one Block), be suppressed at high frequency band, the particularly rising of GHz band medium loss tangent, and, because energy maintenance heat conductivity, thermotolerance, physical strength, the characteristic that synthetic resins such as specific inductivity have, therefore, the resin combination that contains specific a spot of nano-scale carbon tube can be highly suitable for circuit board material, particularly GHz is with the circuit board material of usefulness.

Because nano-scale carbon tube itself has electroconductibility, therefore, also add 5 weight % opening flat 8-134263 number when above when resembling the spy, the electronic component that is formed by the resin combination that obtains also has electroconductibility.Thereby, think can not resemble the spy open flat 8-134263 number described in the resin combination that the electronic component of high frequency band is used the heavy addition nano-scale carbon tube, and do not attempt reducing the dielectric loss angle tangent of high frequency band so far with nano-scale carbon tube yet.But, research according to the inventor, by using the trace of opening flat 8-134263 number described 5 weight % well below above-mentioned spy to add nano-scale carbon tube, obtained this result outside beyond expectation fully of rising who descends and maybe can suppress dielectric loss angle tangent in GHz band medium loss tangent.

The present invention is based on this opinion and further studies repeatedly and finishes, and following electronic component resin combination, electronic component etc. are provided.

Item 1, the charged sub-element resin combination of a kind of GHz, it is characterized in that, it contains at least a resin and the nano-scale carbon tube that is selected from by in the group that compound resin constituted of thermoplastic resin, curable resin and thermoplastic resin and curable resin, and the containing of nano-scale carbon tube stating resin more than proportional is that benchmark is 0.0001～0.4 weight %.

2, as the charged sub-element resin combination of item 1 described GHz, wherein, nano-scale carbon tube is:

(i) multilayer carbon nanotube of single-layer carbon nano-tube or nesting structure;

(ii) amorphous nano-scale carbon tube;

(iii) nano-sheet carbon pipe (Na ノ Off レ one Network カ one ボ Application チ ユ one Block);

(iv) by (a) be selected from the group that the multilayer carbon nanotube by nano-sheet carbon pipe and nesting structure constitutes the carbon pipe and (b) iron carbide or iron constitute, and the pipe of this carbon pipe (a) in the iron-carbon complex of this iron carbide of existence or iron (b) in 10～90% the scope of spatial portion; Or

(the two or more mixture of v) above-mentioned (i)～(iv).

3, as an item 1 or a charged sub-element resin combination of 2 described GHz, wherein, nano-scale carbon tube is an amorphous nano-scale carbon tube, in X-ray diffraction method (incident X-rays: CuK α), utilize the interplanar of the carbon net plane (002) of X-ray diffraction method mensuration to be divided into

More than, diffraction angle (2 θ) is below 25.1 degree, the half breadth of 2 θ bands of a spectrum is more than 3.2 degree.

Item 4, as the charged sub-element resin combination of item 1～3 each described GHz, wherein, resin is for being selected from by polyolefin resin, vibrin, polyamide resin, fluoro-resin, polystyrene resin, polyvinyl chloride (PVC) RESINS, methacrylate resin, acrylate resin, polycarbonate resin, polysulfone resin, polyethersulfone resin, polyphenylene sulfide, polyphenylene oxide resin, ABS resin, polyether-ether-ketone resin, liquid crystalline polymers, thermoplastic polyimide resin, polyetherimide resin, polyacetal, at least a thermoplastic resin in the group that polyarylester (Port リ ア リ レ one ト) and polyethers nitrile resin are constituted.

5, as the charged sub-element resin combination of item 1～3 each described GHz, wherein, resin is at least a curable resin that is selected from the group that is made of thermosetting resin, light-cured resin and electrocuring resin.

6, as the charged sub-element resin combination of item 1 described GHz, wherein, resin is to be selected from by the thermoplastic resin of the cured article that wherein is dispersed with curable resin and wherein to be dispersed with at least a compound resin in the group that curable resin constituted of thermoplastic resin.

7, as the charged sub-element resin combination of item 1～6 each described GHz, wherein, containing of nano-scale carbon tube is proportional, is benchmark with the resin, is 0.001～0.4 weight %.

8, as the charged sub-element resin combination of item 1～6 each described GHz, wherein, nano-scale carbon tube is the multilayer carbon nanotube of aforementioned single-layer carbon nano-tube or nesting structure, and its addition is 0.0001～0.1 weight % with respect to resin.

9, as the charged sub-element resin combination of item 1～6 each described GHz, wherein, nano-scale carbon tube is aforementioned amorphous nano-scale carbon tube, and its addition is 0.0001～0.1 weight % with respect to resin.

10, as the charged sub-element resin combination of item 1～6 each described GHz, wherein, nano-scale carbon tube is aforementioned iron-carbon complex, and its addition is 0.0001～0.4 weight % with respect to resin.

11, as the charged sub-element resin combination of item 1～6 each described GHz, wherein, nano-scale carbon tube is aforementioned nano-sheet carbon pipe, and its addition is 0.0001～0.1 weight % with respect to resin.

Item 12, the charged sub-element of a kind of GHz, it can be by obtaining with resin combination as a charged sub-element of 1～11 each described GHz.

13, as the charged sub-element of item 12 described GHz, it is circuit card, semi-conductor interlayer dielectric or antenna element.

14, as an item 12 or a charged sub-element of 13 described GHz, wherein, the tan δ of resin is reduced to below 0.1 in the GHz band, and resin keeps original other physicals.

15, a kind of reduce electronic component in the GHz band tan δ or be suppressed at the method that the tan δ in the GHz band rises, described electronic component is obtained by at least a resin that is selected from by in the group that compound resin constituted of thermoplastic resin, curable resin and thermoplastic resin and curable resin, the method is characterized in that, in this resin being that the ratio of 0.0001～0.4 weight % is added nano-scale carbon tube with respect to this resin.

16, as item 15 described methods, wherein, nano-scale carbon tube is:

(i) multilayer carbon nanotube of single-layer carbon nano-tube or nesting structure;

(ii) amorphous nano-scale carbon tube;

(iii) nano-sheet carbon pipe;

(iv) by (a) be selected from the group that the multilayer carbon nanotube by nano-sheet carbon pipe and nesting structure constitutes the carbon pipe and (b) iron carbide or iron constitute, and the pipe of this carbon pipe (a) in the iron-carbon complex of this iron carbide of existence or iron (b) in 10～90% the scope of spatial portion; Or

(the two or more mixture of v) above-mentioned (i)～(iv).

17, reduce when a kind of ratio uses resin separately the electronic component that obtains by this resin in the GHz band tan δ or suppress the method that it rises and keeps original other physicals of this resin, this resin is at least a resin that is selected from by in the group that compound resin constituted of thermoplastic resin, curable resin and thermoplastic resin and curable resin, the method is characterized in that, in this resin being that 0.0001～0.4 weight % ratio is added nano-scale carbon tube with respect to this resin.

18, as item 17 described methods, wherein, nano-scale carbon tube is:

(i) multilayer carbon nanotube of single-layer carbon nano-tube or nesting structure;

(ii) amorphous nano-scale carbon tube;

(iii) nano-sheet carbon pipe;

(iv) carbon pipe, (b) iron carbide or the iron that is selected from the group that the multilayer carbon nanotube by nano-sheet carbon pipe and nesting structure constitutes by (a) constitutes, and the pipe of this carbon pipe (a) in the iron-carbon complex of this iron carbide of existence or iron (b) in 10～90% the scope of spatial portion; Or

(the two or more mixture of v) above-mentioned (i)～(iv).

Description of drawings

Fig. 1 is Electronic Speculum (TEM) photo that constitutes 1 of the iron-carbon complex of the carbonaceous material that the special embodiment 1 that opens 2002-338220 number obtains.

Fig. 2 is Electronic Speculum (TEM) photo of the existence of the iron-carbon complex in the carbonaceous material that obtains of the special embodiment 1 that opens 2002-338220 number of expression.

Fig. 3 is Electronic Speculum (TEM) photo of the spy being opened 1 crosscut of iron-carbon complex that 2002-338220 number embodiment 1 obtains.Need to prove that black triangle (▲) expression shown in the photo of Fig. 3 is used for the EDX measuring point of compositional analysis.

Fig. 4 represents the synoptic diagram of the TEM picture of carbon pipe, (a-1) is the synoptic diagram of the TEM picture of cylindric nano-sheet carbon pipe, (a-2) is the synoptic diagram of TEM picture of the multilayer carbon nanotube of nesting structure.

Fig. 5 is the stereographic map of the evaluation that forms of expression embodiment and comparative example manufacturing with the shape of sample, outer conductor and inner wire.

Fig. 6 is the chart of the evaluation that obtains of expression comparative example 1, embodiment 2, embodiment 3 and comparative example 3 with the measurement result of the tan δ of sample.

Fig. 7 is the chart of the evaluation that obtains of expression comparative example 1, embodiment 2 and embodiment 3 with the measurement result of the specific inductivity of sample.

Fig. 8 is the chart of the evaluation that obtains of expression comparative example 1, embodiment 6 and comparative example 4 with the measurement result of the tan δ of sample.

Fig. 9 is the chart of the evaluation that obtains of expression comparative example 1 and embodiment 7 with the measurement result of the tan δ of sample.

Figure 10 is the chart of the evaluation that obtains of expression embodiment 8～11 with the measurement result of the tan δ of sample.

In above-mentioned accompanying drawing, symbol has following connotation.

The picture of TEM longitudinally of 100 nano-sheet carbon pipes

The 110 graphite flake pictures of linearity roughly

200 with the TEM picture of the section of vertical approximate vertical of nano-sheet carbon pipe

210 arcuation graphite flake pictures

300 in the length range longitudinally of the multilayer carbon nanotube of nesting structure successive linearity graphite flake picture

400 with the TEM picture of vertical vertical section of the multilayer carbon nanotube of nesting structure

501 evaluation samples

502 inner wires

503 outer conductors

Embodiment

According to discovering of the inventor, realized above-mentioned purpose by the electronic component that the resin combination that adds above-mentioned nano-scale carbon tube with the minute quantity of 0.001～0.4 weight % and form in resin is made, and by further discovering repeatedly, even the addition of 0.0001 weight % of less amount equally also can be realized above-mentioned purpose.

That is, according to the present invention, the electronic component of making by the resin combination that in resin, adds above-mentioned nano-scale carbon tube and form with the minute quantity of 0.0001～0.4 weight %, in the GHz band, dielectric loss angle tangent (tan δ) ratio reduces when using resin separately, the rising of tan δ in the time of maybe can suppressing to use resin separately, on the other hand, the specific inductivity that resin had originally, thermotolerance, physical strength (for example, tensile strength, the extension at break degree, hardness etc.), rerum naturas such as chemical property, particularly substantial variation can not take place in dielectric characteristics, and keeps former state.

Thereby, when use has the resin of low-k, according to the present invention, the electronic component that the resin combination that forms by mix a small amount of nano-scale carbon tube in the resin with rerum naturas such as low-k, high heat resistance, high mechanical strength is made, in the GHz band, compare with independent use resin, when dielectric loss angle tangent reduces or suppresses its rising, keep rerum naturas such as the original specific inductivity of this resin, high heat resistance, high mechanical strength.

Thereby, by using such resin combination, provide the circuit board material, particularly the GHz band that go for electric, electronics electronic component with circuit board material etc.

In addition, the present invention has following advantage: because by adding nano-scale carbon tube, can not be suppressed at the increase that GHz is with the medium loss tangent in the various characteristics of deterioration resin (dielectric characteristics, thermal property, chemical property, mechanical characteristics), therefore, the resin choice scope increases.

Nano-scale carbon tube

The nano-scale carbon tube that uses among the present invention is meant the carbon pipe with nano-sized diameters, and space segment also can comprise iron etc. in the pipe of this carbon pipe.

Such nano-scale carbon tube, can illustration: (i) amorphous nano-scale carbon tube of single-layer carbon nano-tube or multilayer carbon nanotube, (ii) the applicant's exploitation, (iii) nano-sheet carbon pipe, (iv) by (a) be selected from by the carbon pipe in the group that multilayer carbon nanotube constituted of nano-sheet carbon pipe and nesting structure and (b) iron carbide or iron constitute, and in the pipe of this carbon pipe (a), be filled with iron-carbon complex, (the two or more mixture etc. v) of the iron carbide of (b) or iron in 10～90% the scope of spatial portion.

In the middle of these, particularly above-mentioned amorphous nano-scale carbon tube, nano-sheet carbon pipe and above-mentioned iron-carbon complex, so good dispersion in solvent, binding agent is preferred.These pipes are finely disseminated reason in solvent, binding agent, and are also fully not clear and definite, but because the outermost carbon wire side of these pipes is discontinuous, therefore, are speculated as the high cause of avidity of itself and solvent, binding agent etc.

＜carbon nanotube 〉

Carbon nanotube is the airtight one-tenth piped hollow carbon material of graphite flake (being the carbon atomic layer or the graphite flake of graphite-structure), and its diameter is a nano level, and wall construction has graphite-structure.In the carbon nanotube, wall construction is to be called single-layer carbon nano-tube with the one piece of airtight one-tenth piped of graphite flake material, and many pieces of airtight respectively one-tenth tubuloses of graphite flake, the material that becomes nested shape are called the multilayer carbon nanotube of nesting structure.Among the present invention, the multilayer carbon nanotube of these single-layer carbon nano-tubes and nesting structure can use.

Operable single-layer carbon nano-tube among the present invention, preferred diameter is that about 0.4～about 10nm, length are those of about 1～about 500 μ m, further preferred diameter is that about 0.7～about 5nm, length are those of about 1～about 100 μ m, and preferred especially diameter is that about 0.7～about 2nm, length are those of about 1～about 20 μ m.

In addition, the multilayer carbon nanotube of operable nesting structure among the present invention, preferred diameter is that about 1～about 100nm, length are those of about 1～about 500 μ m, further preferred diameter is that about 1～about 50nm, length are the material of about 1～about 100 μ m, and preferred especially diameter is that about 1～about 40nm, length are those of about 1～about 20 μ m.

＜amorphous nano-scale carbon tube 〉

In addition, above-mentioned amorphous nano-scale carbon tube, as described in WO 00/40509 (No. the 3355442nd, Japanese Patent), be to have the main framing that is made of carbon, diameter is 0.1～1000nm, has the nano-scale carbon tube of amorphous structure, it is characterized in that, form with linearity is in X-ray diffraction method (incident X-rays: CuK α), utilize the interplanar of the carbon net plane (002) of X-ray diffraction method mensuration every (d002) to be More than, particularly More than, diffraction angle (2 θ) is below 25.1 degree, particularly below 24.1 degree, the half breadth of 2 θ band is more than 3.2 degree, particularly more than 7.0 degree.

This amorphous nano-scale carbon tube can obtain by following operation: comprising in the presence of the muriatic at least a catalyzer of metals such as magnesium, iron, cobalt, nickel that pyrolytic resin, for example tetrafluoroethylene, polyvinylidene chloride, polyvinylidene difluoride (PVDF), polyvinyl alcohol that decomposition temperature is 200～900 ℃ etc. excites processing.

As the shape of the pyrolytic resin of starting raw material, can be membranaceous or arbitrary shape such as sheet, Powdered, bulk.For example, when on substrate, obtaining forming the carbon material of membranaceous amorphous nano-scale carbon tube,, excite processing to get final product under suitable condition applying on the substrate or having placed under the pyrolytic state of resin.

But this excites the processing example as follows: for example, in rare gas element, preferably heating under about 450～about 1800 ℃ temperature range and more than the heat decomposition temperature at raw material, under the temperature range of room temperature～about 3000 ℃ and more than the raw material heat decomposition temperature, carry out the processing of plasma treatment etc.

The amorphous nano-scale carbon tube that uses among the present invention is the nano level carbon nanotube with amorphous structure (non-crystal structure), is the hollow linearity, has the highly micropore of control.Its shape mainly is cylinder, rectangular prism etc., and at least one of front end do not have cap (opening) mostly.Front end is when remaining silent state, and it is plane that its shape is mostly.

The external diameter of this amorphous nano-scale carbon tube is usually in the scope of about 1～about 1000nm, preferably in the scope of about 1～about 200nm, more preferably in the scope of about 1～about 100nm.Its long-width ratio (length/diameter of pipe) is more than 2 times, is preferably more than 5 times.

At this, so-called " amorphous structure " is meant not to be the graphite matter structure that continuous carbon-coating constituted by regularly arranged carbon atom, but the carbonaceous structure that is constituted by irregular carbon net plane, a plurality of trickle graphite flakes are being arranged brokenly.The picture that forms from the transmission type microscope of utilizing as the analytical procedure of representative utilizes the nano-scale carbon tube of non-crystal structure of the present invention as can be seen, and the width of the in-plane of carbon net plane is littler than amorphous nano-scale carbon tube diameter.So, amorphous nano-scale carbon tube is not graphite-structure but amorphous structure that a lot of fine graphite flake (carbon wire side) distributes brokenly because its wall portion has, therefore, it is discontinuous in managing longitudinally length range to constitute outermost carbon wire side, forms discontinuous shape.The length that particularly constitutes outermost carbon wire side is lower than 20nm, particularly is lower than 5nm.

Amorphous carbon does not show X-ray diffraction usually, and shows reflection widely.In graphite matter structure, because being regularly, piles up the carbon net plane, therefore, the carbon net plane is (d at interval ₀₀₂) narrow down, reflect widely to high corner side (2 θ) and move, and narrow down gradually (half breadth of 2 θ band narrows down), can be used as d ₀₀₂Diffracted ray is observed (when piling up regularly because of the position of graphite relation then

)

Relative with it, as mentioned above, non-crystal structure does not show usually and utilizes X-ray diffraction, and but partly shows very weak interference capability scattering.In X-ray diffraction method (incident X-rays=CuK α), utilize the theoretical crystallographic characteristics of the amorphous nano-scale carbon tube of the present invention that X-ray diffraction method measures, be regulation as described below: the carbon net plane is (d at interval ₀₀₂) be

More than, more preferably

More than; Diffraction angle (2 θ) is below 25.1 degree, more preferably below 24.1 degree; The half breadth of aforementioned 2 θ band is more than 3.2 degree, more preferably more than 7.0 degree.

In typical case, the amorphous nano-scale carbon tube that uses among the present invention, the diffraction angle of its X-ray diffraction (2 θ) is in the scope of 18.9～22.6 degree, and the carbon net plane is (d at interval ₀₀₂)

Scope in, the half breadth of 2 θ band is in the scopes of 7.6～8.2 degree.

Term " linear " speech as expression amorphous nano-scale carbon tube shape of the present invention, be defined as follows: that is, establish utilize the amorphous nano-scale carbon tube picture that transmission type microscope measures length for L, the length of establishing when stretching this amorphous nano-scale carbon tube is L ₀The time, L/L ₀It is the style characteristic more than 0.9.

The tube wall part of this amorphous nano-scale carbon tube, it is the non-crystal structure that constitutes by a plurality of fine carbon net plane (graphite flake) that on all directions, is orientated, owing to the carbon interplanar of these carbon net planes every having active site, therefore, it has the advantage with the excellent affinity of resin.

＜iron-carbon complex 〉

In addition, iron-the carbon complex that uses among the present invention, open as described in the 2002-338220 communique (No. 3569806 communique of patent) as the spy, by (a) be selected from by the carbon pipe in the group that multilayer carbon nanotube constituted of nano-sheet carbon pipe and nesting structure and (b) iron carbide or iron constitute, and in the pipe of this carbon pipe (a), be filled with the iron carbide or the iron of (b) in 10～90% the scope of spatial portion.That is, it is characterized in that, not completely filled in 100% the scope of spatial portion in the pipe, above-mentioned iron carbide or iron are filled in 10～90% the scope of spatial portion in its pipe (being partially filled).Wall portion is a nano-sheet carbon pipe of piecing shape or papier-mache shape (so-called paper mache shape) together.

In the application's claims and specification sheets, so-called " nano-sheet carbon pipe " is meant to comprise that many pieces of (being generally usually many) flake graphite sheets assemble the carbon tubulation of the aggregate of the graphite flake of piecing shape or papier-mache shape (paper mache shape) formation together.

This iron-carbon complex, according to open the described method of 2002-338220 communique as the spy, utilization comprises

(1) in inert gas atmosphere, adjusts pressure to 10 ^-5Pa～200kPa, the oxygen concn of adjusting in the Reaktionsofen make that establishing the Reaktionsofen volume is A (liter), the ratio B/A when the oxygen amount is B (Ncc) is 1 * 10 ^-10～1 * 10 ^-1Reaktionsofen in, iron halide is heated to 600～900 ℃ operation; And

(2) in above-mentioned Reaktionsofen, introduce rare gas element, at pressure 10 ^-5Pa～200kPa introduces the pyrolytic carbon source down, carries out heating treatment step at 600～900 ℃

Manufacture method make.

At this, the unit " Ncc " of oxygen amount B is meant the gas volume (cc) when converting 25 ℃ of standard state to.

This iron-carbon complex is selected from the carbon pipe in the group that the multilayer carbon nanotube by nano-sheet carbon pipe and nesting structure constitutes by (a) and (b) iron carbide or iron constitute, and spatial portion (i.e. the space that is surrounded by tube wall) is not in fact a completely filled in this carbon pipe, the part of this spatial portion, more specifically is about 10～about 90%, particularly about 30～about 80%, preferred about 40～about 70% to utilize iron carbide or iron to fill.

In the present invention in the iron-carbon complex of Shi Yonging, open as described in the 2002-338220 communique as the spy, carbon part becomes nano-sheet carbon pipe when carrying out manufacturing process (1) and (2) back with specific speed cooling; After carrying out manufacturing process (1) and (2),,, become the multilayer carbon nanotube of nesting structure with specific speed of cooling cooling by in rare gas element, carrying out heat treated.

＜(a-1) nano-sheet carbon pipe 〉

Iron-the carbon complex that is made of nano-scale carbon tube and iron carbide or iron of the present invention is cylindric typically, with transmission type microscope (TEM) photo of the section of vertical approximate vertical of this cylindric iron-carbon complex (opening iron-carbon complex that 2002-338220 number embodiment 1 obtains) by the spy as shown in Figure 3, lateral TEM photo is as shown in Figure 1.

In addition, Fig. 4 (a-1) is the synoptic diagram of the TEM picture of this cylindric nano-scale carbon tube.In (a-1) of Fig. 4,100 schematically represent the picture of TEM longitudinally of nano-sheet carbon pipe, the 200 TEM pictures of expression and the section of vertical approximate vertical of nano-sheet carbon pipe schematically.

The nano-sheet carbon pipe that constitutes the iron-carbon complex that uses among the present invention has the hollow cylindrical form usually.When by its section of tem observation, arcuation graphite flake image set synthesizes concentric circles, each graphite flake looks like to form discontinuous ring, with tem observation its when vertical, being roughly, the graphite flake of linearity looks like to be roughly parallel to vertical and is arranged in the multilayer shape, each graphite flake picture length range in the vertical is interior discontinuous, becomes discontinuous shape.

In more detail, constitute the nano-sheet carbon pipe of the iron-carbon complex that uses among the present invention, as Fig. 3 and Fig. 4 (a-1) 200 shown in, with tem observation with it during vertical vertical section, the synthetic concentric circles (tubulose of multilayered structure) of most arcuation graphite flake image sets, each graphite flake picture for example shown in 210,214, does not form airtight successive ring fully, but the discontinuous ring that is interrupted in the middle of forming.Part graphite flake picture also has branch sometimes shown in 211.For point of discontinuity, constitute a plurality of arcuation TEM pictures of a discontinuous ring, both just like Fig. 4 (a-1) 222 shown in the situation of layer structure division disorder, again just like the situation that has the gap between the graphite flake picture shown in 223 and adjacent, but the most arcuation graphite flake pictures with tem observation form multi-lamellar tubular structure as a whole.

In addition, as Fig. 4 (a-1) 100 shown in, during with tem observation nano-sheet carbon pipe vertical, vertical almost parallel of iron-carbon complex that many roughly linearly graphite flake pictures and the present invention use also is arranged in the multilayer shape, but each graphite flake as 110 iron-carbon complex vertically on discontinuous in length range, discontinuous shape in the middle of becoming.Part graphite flake picture as Fig. 4 (a-1) 111 shown in, branch is also arranged sometimes.In addition, for point of discontinuity, in being arranged in lamellated TEM picture, the TEM picture of a lipostrat both just like Fig. 4 (a-1) 112 shown in the partly overlapping at least situation of adjacent graphite flake picture, again just like the situation that looks like to separate a little shown in 113 with adjacent graphite flake, but the TEM picture of many roughly linearities forms multilayered structure as a whole.

The structure of this nano-sheet carbon pipe of the present invention is compared with existing multilayer carbon nanotube, has a great difference.That is, as Fig. 4 (a-2) 400 shown in, multilayer carbon nanotube with regard to nesting structure, TEM picture of vertical vertical section with it shown in 410, is the concentric circles pipe that constitutes circular in fact fully TEM picture, and, as Fig. 4 (a-2) 300 shown in, its longitudinally in the length range successive linearity graphite flake be the structure (structure of concentric(al) circles tubular or nested shape) that is arranged in parallel as 310 etc.

As known from the above, details is not clear and definite fully as yet, but just constitute the nano-sheet carbon pipe of the iron-carbon complex that uses among the present invention, but seem that it has following structure: many flaky graphite flakes are pieces shape together or the papier-mache shape is overlapping and form pipe together.

Of the present invention by nano-sheet carbon pipe and the iron carbide that is included in spatial portion in the pipe or iron-carbon complex that iron constitutes, the complex body that comprises metal with spatial portion in the pipe of the multilayer carbon nanotube of No. 2546114 described nesting structure of patent is compared, and in the configuration aspects of carbon pipe a great difference is arranged.

When constituting the nano-sheet carbon pipe of the iron-carbon complex that uses among the present invention with tem observation, vertical with regard to the graphite flake picture of the many basic linearities that are orientated with regard to it, the length of each graphite flake picture is generally about 2～about 500nm, particularly about 10～about 100nm.That is, as Fig. 4 (a-1) 100 shown in, with the TEM picture of the graphite flake of the basic linearity shown in 110, many TEM pictures that constitute the wall portion of nano-sheet carbon pipe together, the length of the graphite flake picture of each basic linearity is generally about 2～about 500nm, particularly about 10～about 100nm.

So, in iron-carbon complex, constitute the outermost layer of the nano-sheet carbon pipe of its wall portion, in that discontinuous graphite flake forms in the length range by managing longitudinally, its outermost carbon wire side length is generally about 2～about 500nm, is in particular about 10～about 100nm.

The carbon part of the wall portion of the nano-sheet carbon pipe of the iron-carbon complex that uses among formation the present invention, as mentioned above, many flaky graphite flake orientations in the vertical, form tubulose as a whole, when utilizing X-ray diffraction to measure, its mean distance (d002) that has between the carbon wire side is the following graphite matter structure of 0.34nm.

In addition, the thickness of the wall portion that is made of the nano-sheet carbon pipe of the iron-carbon complex that uses among the present invention is generally below the 49nm, and particularly about 0.1～about 20nm is preferably about 1～about 10nm, comes down in length range uniformly.

＜(a-2) multilayer carbon nanotube of nesting structure 〉

As previously mentioned, carrying out carrying out specific heating process behind manufacturing process (1) and (2), the carbon pipe in the iron-carbon complex that obtains thus forms the multilayer carbon nanotube of nesting structure.

The multilayer carbon nanotube of the nesting structure that obtains like this, as Fig. 4 (a-2) 400 shown in, TEM picture of vertical vertical section with it, it is the pipe that constitutes round in fact fully concentric circles, and, its longitudinally in the length range successive graphite flake look like to be the structure (structure of concentric(al) circles tubular or nested shape) that is arranged in parallel.

The carbonaceous part of the wall portion of the multilayer carbon nanotube of the nesting structure of the iron-carbon complex that uses among formation the present invention, when utilizing X-ray diffraction method to measure, its mean distance (d002) that has between the carbon wire side is the following graphite matter structure of 0.34nm.

In addition, the thickness of the wall portion that is made of the multilayer carbon nanotube of the nesting structure of the iron-carbon complex that uses among the present invention is generally below the 49nm, and particularly about 0.1～about 20nm is preferably about 1～about 10nm, comes down in length range uniformly.

＜the iron carbide or the iron that (b) comprise 〉

Be selected from this manual by the iron carbide of spatial portion in the carbon pipe in the group that multilayer carbon nanotube constituted of above-mentioned nano-sheet carbon pipe and nesting structure or the filling ratio (10～90%) of iron, with the iron-carbon complex that uses among transmission electron microscopy the present invention obtain, the area of the picture of iron carbide or iron filling part is with respect to the ratio of the area of the picture of the spatial portion of each carbon pipe (i.e. the space that is surrounded by the tube wall of carbon pipe).

The filling morphology of iron carbide or iron has form that spatial portion is filled continuously in the carbon pipe and the form that spatial portion is intermittently filled in the carbon pipe etc., but is interrupted the filling basically.Thereby the iron-carbon complex that uses among the present invention is meant the carbon complex that comprises metal or comprises the carbon complex of iron cpd or comprise iron carbide or the carbon complex of iron.

In addition, iron carbide that comprises in the iron-carbon complex that uses among the present invention or iron, the carbon pipe vertically on orientation, the crystallinity height, the area of the TEM picture of crystallinity iron carbide or iron is generally about 90～about 100%, particularly about 95～about 100% with respect to the ratio (hereinafter referred to as " crystallization rate ") of the area of the TEM picture of the scope of iron carbide or iron filling.

The high this point of the iron carbide that comprises or the crystallinity of iron is reticulation according to the TEM picture of inclusion when tem observation is carried out in the side of iron-carbon complex of the present invention, and to arrange this point be clearly, also is clearly according to obtain clear and definite diffraction pattern this point in electron beam diffraction.

In addition, comprise iron carbide or iron this point in the iron-carbon complex that uses among the present invention, utilize Electronic Speculum, EDX (energy dispersion type X-ray detector) to confirm at an easy rate.

The global shape of＜iron-carbon complex 〉

Iron-the carbon complex that uses among the present invention since bending less, linearly, the thickness of wall portion roughly has certain uniform thickness in length range, therefore, have uniform shape in length range.It is shaped as column, it is cylindric to be mainly.

The external diameter of iron-carbon complex of the present invention is generally about 1～about 100nm, the particularly scope of about 1～about 50nm, the scope of preferred about 1～about 30nm, the more preferably from about scope of 10～about 30nm.The length of pipe (L) is generally about 5～about 10000, particularly about 10～about 1000 with respect to the long-width ratio (L/D) of external diameter (D).

A term " linearity " speech of the shape of the iron-carbon complex that uses among the present invention as expression, be defined as follows: that is, utilize transmission type microscope to observe the carbonaceous material that comprises the iron-carbon complex that uses among the present invention in the square scope of 200～2000nm, the length of establishing picture is W, this length when looking like to be in line shape that stretches is W ₀The time, compare W/W ₀Be more than 0.8, the style characteristic more than 0.9 particularly.

Iron-the carbon complex that uses among the present invention has following character as a whole during material.That is, in the present invention, in the pipe of the carbon pipe of the multilayer carbon nanotube that is selected from aforesaid nano-sheet carbon pipe and nesting structure, be filled with the iron-carbon complex of iron or iron carbide in 10～90% of spatial portion the scope, not to utilize the microscope only can inadequate observed trace, but comprise the integral material of many these iron-carbon complexes, should be called the carbonaceous material that comprises iron-carbon complex or to comprise iron carbide or the material shape of the carbonaceous material of iron obtains in a large number.

The electromicroscopic photograph of opening the carbonaceous material of the present invention that comprises the iron carbide that spatial portion is filled in nano-sheet carbon pipe and the pipe that the embodiment 1 of 2002-338220 communique makes by the spy as shown in Figure 2.

As shown in Figure 2, in the carbonaceous material of the iron-carbon complex that contains the present invention's use, basically, in nearly all (particularly 99% or more than it) carbon pipe, generally, in 10～90% the scope of its spatial portion (i.e. the space that surrounds by the tube wall of carbon pipe), be filled with iron carbide or iron, and the carbon pipe that spatial portion does not have to fill is actually non-existent.But, under different situations, often also be mixed with the carbon pipe of not filling iron carbide or iron of trace.

In addition, in carbonaceous material of the present invention, 10～90% iron-carbon complexes that are filled with iron or iron carbide of spatial portion are the main composition compositions in the aforesaid carbon pipe, but beyond iron-carbon complex of the present invention, comprise tin etc. sometimes.At this moment, remove iron-carbon complex of the present invention composition in addition, can improve the purity of the iron-carbon complex in the carbonaceous material of the present invention, obtain the carbonaceous material that in fact only constitutes by the iron-carbon complex that uses among the present invention.

In addition, different with the material that only can utilize microscope can trace to confirm in the past, can synthesize in a large number owing to include the carbonaceous material of the iron-carbon complex that uses among the present invention, therefore, can at an easy rate its weight be set in more than the 1mg.

Carbonaceous material of the present invention is being 25mm to this carbonaceous material 1mg ²During the powder x-ray diffraction of the X ray of above irradiated area irradiation CuK α is measured, show that with belonging in the peak of 40 °＜2 θ＜50 ° of the iron that comprises or iron carbide the integrated intensity at the peak of the strongest integrated intensity is set at Ia, when the integrated intensity at peak that belongs to 26 °＜2 θ＜27 ° of the mean distance (d002) between the carbon wire side of carbon pipe is set at Ib, the ratio R of Ia and Ib (=Ia/Ib) be preferably about 0.35～about 5, preferred about especially 0.5～about 4, more preferably from about 1～about 3.

In this manual, the ratio with above-mentioned Ia/Ib is called R.This R value is illustrated in by X-ray diffraction method and will comprises the carbonaceous material of the iron-carbon complex that uses among the present invention at 25mm ²When above x-ray bombardment area is observed, because the mean value as carbonaceous material integral body is observed peak intensity, thereby it is not to comprise rate or filling ratio in 1 iron-carbon complex can measuring by tem analysis, but expression is as the iron carbide or the iron filling ratio of the carbonaceous material integral body of the aggregation of iron-carbon complex or comprise the mean value of rate.

Need to prove, mean cut-off rate as the carbonaceous material integral body that comprises a plurality of iron-carbon complexes of the present invention, can obtain by the following method: with a plurality of visuals field of tem observation, be determined at the iron carbide in a plurality of iron-carbon complexes of each visual field observing or the mean cut-off rate of iron, the mean value of further calculating the mean cut-off rate in a plurality of visuals field.When measuring, be about 10～about 90%, particularly about 40～about 70% as the iron carbide of the carbonaceous material integral body that comprises the iron-carbon complex that uses among the present invention or the mean cut-off rate of iron with such method.

＜nano-sheet carbon pipe 〉

By above-mentioned iron or iron carbide iron-carbon complex that space segment comprises in the pipe of nano-sheet carbon pipe are carried out acid treatment, iron or the iron carbide that comprises removed in dissolving, and there is not the nano-sheet carbon pipe of the hollow of iron or iron carbide in spatial portion in can obtaining managing.

The acid of using in the above-mentioned acid treatment can illustration: hydrochloric acid, sulfuric acid, nitric acid, fluoric acid etc., the preferably about 0.1～about 2N of its concentration.Acid-treated method, can utilize the whole bag of tricks to carry out, for example, in the hydrochloric acid 100ml of 1N, the ferruginous nano-sheet carbon of the bag pipe that disperses 1g was handled 6 hours in stirring at room, after the filtering separation, further handle equally 2 times, can obtain the nano-sheet carbon pipe of hollow by hydrochloric acid 100ml with 1N.

Even utilize this acid treatment, the basic structure of nano-sheet carbon pipe does not have substantial variations yet.Therefore, even spatial portion does not exist in the nano-sheet carbon pipe of hollow of iron or iron carbide in pipe, the length that constitutes its outmost carbon wire side is below the 500nm, 2～500nm particularly, preferred 10～100nm.

Resin

The present invention uses at least a in the group that the compound resin be selected from various thermoplastic resins, curable resin and thermoplastic resin that field of electrical components uses and curable resin constitutes.

The thermoplastic resin that uses among the present invention, can use the material of broad range, can example for example have: polyolefin resin is (for example: straight chain shape polyolefin resines such as polyvinyl resin, acrylic resin, poly-1-butylene resin, poly(4-methyl-1-pentene) resin; The 5-methylpentene resin, the cyclic polyolefin resin that comprises cyclic olefin in the compositions such as polynorbornene resin), vibrin (for example: polyethylene terephthalate, polybutylene terephthalate, PEN polyethyleneglycol block copolymer etc.), polyamide resin (for example: nylon 4, nylon 6, nylon 66, NYLON610, nylon 12 etc.), fluoro-resin (for example: teflon resin, poly-trifluoro-ethylene resin etc. and Tefzel, tetrafluoroethylene/hexafluoropropylene copolymer, hot melt voltinism fluoro-resin such as tetrafluoroethylene/perfluoro alkoxy vinyl ethers multipolymer), polystyrene resin, polyvinyl chloride (PVC) RESINS, methacrylate resin or acrylate resin are (for example: polymethylmethacrylate, polymethyl acrylate etc.), polycarbonate resin, polysulfone resin, polyethersulfone resin, polyphenylene sulfide, polyphenylene oxide resinoid (polyphenylene oxide particularly; Added a small amount of polystyrene or styrene butadiene class elastomerics and improved polyphenylene oxide resin of shock-resistance and plasticity etc.), ABS resin (for example: improved the thermotolerance ABS resin of heat-drawn wire etc. by the copolymerization maleimide), polyether-ether-ketone resin, liquid crystalline polymers (for example thermotropic liquor polyester resin etc.), thermoplastic polyimide resin, polyetherimide resin, polyacetal, polyarylester resin, polyethers nitrile resin etc.Among the present invention, can use a kind of in these thermoplastic resins separately, also can use wherein two or more simultaneously.

In addition, the curable resin that uses among the present invention exemplifies thermosetting resin, light-cured resin, electrocuring resin etc. for representative, these resins all have processing, when being shaped by giving solidified character with external energy such as heat, light, electron beam.

Thermosetting resin for example has: Resins, epoxy (for example: the cresols novolac epoxy resin, the phenol novolac epoxy resin, biphenyl type epoxy resin, by dihydroxyphenyl propane, the various novolac epoxy resins of synthetic such as Resorcinol, bisphenol A type epoxy resin, brominated bisphenol a type epoxy resin, the wire aliphatic epoxy resin, alicyclic epoxy resin, hetero ring type Resins, epoxy, halogenated epoxy resin, volution formula Resins, epoxy etc.), diallyl phthalate resin, silicone resin, resol, unsaturated polyester resin, polyimide resin, urethane resin, furane resin, urea resin, melamine resin, the triazines resin (for example: bismaleimide-triazine resin (BT resin) etc.), the solidified nature polyphenylene oxide resin, bridging property polyphenylene oxide, maleimide resin, Synolac, xylene resin etc.Among the present invention, can use a kind of in these thermosetting resins separately, also can use wherein two or more simultaneously.

These thermosetting resins, can add polymerization atarting material (solidifying agent) as required uses, for example, curing agent for epoxy resin has: amine curing agent, polyamide-based solidifying agent, acid anhydride type curing agent, potentiality solidifying agent etc., having can be suitable with the compound of the active group of epoxy reaction (preferred amino, anhydride group, azido-, hydroxyl).More specifically, amine curing agent for example has: fatty amine, cycloaliphatic amines, aromatic amine etc.; Polyamide-based solidifying agent for example has: daiamid etc.; Acid anhydride type curing agent for example has: aliphatic anhydride, ester ring type acid anhydrides, aromatic anhydride, halogen acid anhydrides etc.; The potentiality solidifying agent for example has: high-melting-point active dydrogen compounds (diamines diamide, organic acid dihydrazide etc.), tertiary amine imidazole salts (salt of Lewis acid Bronsted acid etc.), but be not limited to these.The silicone resin solidifying agent for example has: aminooxy silane etc.The solidifying agent of unsaturated polyester resin for example has: benzoyl peroxide (BPO) and methyl ethyl ketone peroxide (MEKPO), organo-peroxide (hydrogen peroxide, dialkyl peroxide, peroxyester, diacyl peroxide, peroxy dicarbonate, ketal peroxide, ketone peroxide) etc.

These solidifying agent get final product with habitual usage quantity use for each thermoset tree, generally, are about 0.3～about 5 weight parts with respect to thermosetting resin 100 weight parts, are preferably about 1～about 3 weight parts especially.

The curable resin that uses among the present invention can be a light-cured resin of giving light solidified.Can use known light-cured resin, for example: acrylic resin, silicone resin, ester resin etc.Representational for example have: as the ultraviolet curing resin that has acryl in the molecule monomer as follows or the mixture of oligopolymer or polymkeric substance etc.For example: the oligopolymer or the polymkeric substance of epoxy acrylate class, urethane acrylate class, polyester acrylate class, polyalcohol acrylate class.Also have as simple function, difunctionality or polyfunctional polymerizable (methyl) acrylic acid or the like, monomer or oligopolymer or polymkeric substance such as tetrahydrofurfuryl acrylate, vinylformic acid 2-hydroxyl ethyl ester, vinylformic acid 2-hydroxyl-3-benzene oxygen propyl ester, polyethyleneglycol diacrylate, polypropyleneglycol diacrylate, Viscoat 295, pentaerythritol triacrylate, tetramethylol methane tetraacrylate are for example arranged.These light-cured resins can be used alone, and also can use two or more simultaneously.

Need to prove, also can cooperate the Photoepolymerizationinitiater initiater (if necessary, using photopolymerization promoter simultaneously) that adds usually in the light-cured resin with normally used amount.

Photopolymerization causes choosing and absorbs the material that ultraviolet ray is easy to generate free radical, can use phenyl methyl ketone class, thioxanthene ketone, benzene idol

The known material of class, peroxide.For example can enumerate: diethoxy phenyl methyl ketone, 4-phenoxy group Er Lvyixianben, benzene idol

, benzene idol

Ether, benzene idol

Isopropyl ether, dibenzoyl dimethyl ketal, benzophenone, 4-phenyl benzophenone, acrylated benzophenone, thioxanthone, 2-ethyl-anthraquinone etc.

The usage quantity of Photoepolymerizationinitiater initiater for each light-cured resin, gets final product with habitual usage quantity use, generally, is about 0.3～about 5 weight parts with respect to light-cured resin 100 weight parts, is preferably about 1～about 3 weight parts especially.

In addition, photopolymerization promoter is compared during with independent use Photoepolymerizationinitiater initiater, is to promote initiation reaction, be cured the material of reaction effectively, can use known light-initiated auxiliary agents such as aliphatics, aromatic amine.For example have: trolamine, N methyldiethanol amine, michaelis ketone, 4,4-diethylin benzophenone etc.

When using photopolymerization promoter, its usage quantity for each light-cured resin, gets final product with habitual usage quantity use, generally, is about 0.3～about 5 weight parts with respect to light-cured resin 100 weight parts, is preferably about 1～about 3 weight parts especially.

In addition, the curable resin that uses among the present invention also can be the electrocuring resin.Can use existing known electrocuring resin, can illustratively for example have: (A) acrylate compounds of aliphatics, alicyclic and aromatic 1～6 yuan of alcohol and polyalkylene glycol; (B) on aliphatics, alicyclic, aromatic 1～6 yuan of alcohol addition the acrylate compounds of material of alkylene oxide; (C) polypropylene acyl group alkyl phosphate class; (D) carboxylic acid and polyvalent alcohol and acrylic acid resultant of reaction class; (E) isocyanic ester and polyvalent alcohol and acrylic acid resultant of reaction class; (F) epoxy compounds and acrylic acid resultant of reaction; (G) epoxy compounds and polyvalent alcohol and acrylic acid resultant of reaction class etc.

More specifically, the electrocuring resin is preferably selected from the bisphenol a diacrylate of polyethylene oxide Epicholorohydrin modification, the dicyclohexyl acrylate, the polyethyleneglycol diacrylate of Epicholorohydrin modification, 1, the 6-hexanediyl ester, hydroxyl trimethylacetic acid ester neopentylglycol diacrylate, the Nonylphenoxy polyethylene glycol acrylate, the phenoxy group p thiodipropionic acid ester of oxyethane modification, the phthalic acid acrylate of oxyethane modification, the PBAA ester, the tetrahydrofurfuryl acrylate of caprolactone modification, three (acrylyl oxy-ethyl) isocyanuric acid ester, Viscoat 295, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol acrylate, polyethyleneglycol diacrylate, 1,4-butadiene glycol diacrylate, the material of the trimethylolpropane diacrylate of neopentylglycol diacrylate and neopentyl glycol modification etc.

In the present invention, can use thermoplastic resin and curable resin simultaneously with the form of compound resin.At this moment, this compound resin for example can use with the form of the thermoplastic resin that wherein is dispersed with curable resin, also can use with the form of the curable resin that wherein is dispersed with thermoplastic resin.

The resin combination that above-mentioned illustrative resin and nano-scale carbon tube constitute, make tan δ be lower than original resin (fertile material), other physicals specific inductivity in addition, physical strength, thermotolerance etc. maintain peer-level with original resin, its result provides the electronic component that is suitable for each purposes.

In above-mentioned resin, preferred:

(1) thermoplastic resins such as polyolefin resin, vibrin, polyamide resin, fluoro-resin, polystyrene resin, polyvinyl chloride (PVC) RESINS, poly-(methyl) methyl acrylate resin, polycarbonate resin, polyethersulfone resin;

(2) curable resins such as polyimide resin, dimaleimide cyanate resin (BT resin), bridging property polyphenylene oxide, solidified nature polyphenylene oxide, resol, melamine resin, urea resin, unsaturated polyester resin, Synolac, Phthalic acid, diallyl ester, xylene resin, Resins, epoxy, epoxy acrylate resinoid, urethane acrylate resinoid, polyester acrylic esters resin, polyalcohol acrylate resinoid.

Resin combination

Resin combination of the present invention contains aforementioned resin and aforementioned nano-scale carbon tube.

Resin combination of the present invention is characterised in that, the addition of nano-scale carbon tube is a benchmark with the resin, is the ratio of 0.0001～0.4 weight %.Make the mechanism of the dielectric loss angle tangent reduction in the GHz band by the nano-scale carbon tube that adds such denier, still indeterminate at present, but think that nano-scale carbon tube physically compensates the cause of the dipole electric field change of the polarity gene dielectric depolarization generation that is included in the resin owing to pass through the nano-scale carbon tube homodisperse of denier.When the use level of nano-scale carbon tube was lower than 0.0001 weight %, a little less than its effect, when surpassing 0.4 weight %, dielectric loss angle tangent can rise.

The addition of nano-scale carbon tube is 0.0005～0.4 weight % with respect to resin, is preferably 0.001～0.4 weight %, preferred especially 0.001～0.3 weight %.It is 0.001～0.2 weight % that further preferred addition with nano-scale carbon tube is set at respect to resin, particularly 0.001～0.1 weight %.

In addition, when nano-scale carbon tube was the multilayer carbon nanotube of aforementioned carbon nanotube or nesting structure, its addition was 0.0001～0.1 weight % with respect to resin, preferred especially 0.0001～0.05 weight %.

When nano-scale carbon tube was aforementioned amorphous nano-scale carbon tube, its addition was 0.0001～0.1 weight % with respect to resin, preferred especially 0.0001～0.05 weight %.

When nano-scale carbon tube was an aforementioned iron-carbon complex, its addition was 0.0001～0.4 weight % with respect to resin, preferred especially 0.01～0.4 weight %.

When nano-scale carbon tube was aforementioned nano-sheet carbon pipe, its addition was 0.0001～0.1 weight % with respect to resin, preferred especially 0.0001～0.05 weight %.

Need to prove, in the present invention, the resin that uses is during as thermosetting resin, the addition of nano-scale carbon tube, weight (when using solidifying agent in the curing of this thermosetting resin, the gross weight of the weight of thermosetting resin and the weight of solidifying agent) with thermosetting resin is set for benchmark.For example, when using Resins, epoxy as thermosetting resin, the gross weight of the weight of the solidifying agent that uses in solidifying with respect to the weight of this Resins, epoxy and its, the addition of setting nano-scale carbon tube is the scope of aforementioned 0.0001～0.4 weight %.

Equally, the resin that uses among the present invention is during as light-cured resin, the addition of nano-scale carbon tube, with respect to the weight of (a) optical polymerism resinous principle (oligopolymer, monomer etc.), and the gross weight of the weight of the Photoepolymerizationinitiater initiater that (b) in the curing of this light-cured resin, uses (and when using photopolymerization promoter, adding the weight of photopolymerization promoter) be that benchmark is set.For example, when using the ultraviolet curing based acrylic resin as resin, the gross weight of the weight (and weight of the photopolymerization promoter of using as required) of the Photoepolymerizationinitiater initiater that uses during with respect to the weight of (a) this ultraviolet curing based acrylic resin and (b) it solidifies, the addition of setting nano-scale carbon tube is the scope of aforesaid 0.0001～0.4 weight %.

Can adopt the whole bag of tricks in order to make resin combination of the present invention.Can illustratively for example have: when using thermoplastic resin, make thermoplastic resin be dissolved in the solvent that can dissolve this resin and obtain the thermoplastic resin solution, add nano-scale carbon tube therein, from the mixture that obtains, heat up in a steamer the method for desolvating; Or the thermoplastic resin heating and melting is become liquid, and adding nano-scale carbon tube therein, pugging mullering is to its uniform method etc.

In addition, when using thermosetting resin, owing to, therefore, can adopt the method for hybrid nanoscale carbon pipe in the thermosetting resin before curing with liquid state normally before thermosetting resin cured.Equally, owing to also being liquid state usually before light-cured resin, the electrocuring resin solidification, therefore, can adopt the method for hybrid nanoscale carbon pipe in the resin before curing.

In the resin combination of the present invention, as required, in the scope that does not influence effect of the present invention, also can add the various additives such as antioxidant that use in this field.

Composition of the present invention can obtain by mixing above-mentioned resin, nano-scale carbon tube and above-mentioned additive as required.Blending means can be used well-known method, for example, can adopt the method for using ceramic 3 roller mills, mould wash mixer, planetary mills etc.

Electronic component

Composition of the present invention since provide possess low-k, the resin of low dielectric loss angle tangent, high heat resistance and high mechanical strength, therefore can be suitably as circuit board material, particularly GHz band circuit board material electric, electronics.Especially, owing to can under deterioration has not been improved the situation of the characteristic that the resin of various characteristics (dielectric characteristics, thermal property, chemical property, mechanical characteristics) has, suppress the increase of GHz band medium loss tangent, therefore, can make the resin choice increase.

At this, electronic component of the present invention has above-mentioned characteristic in the GHz of the wide region more than the 1GHz band, generally, in the band of the scope of 1～20GHz, particularly 1～10GHz, can get aforementioned excellent results.

Specifically, composition of the present invention can be suitably as the high-frequency apparatus of representatives such as for example satellite broadcasting relevant device and the printing printed circuit board material of information processing device.And composition of the present invention can for example used in the broad range of device elements such as IC socket and junctor from base components such as package semiconductor field, resistor, switch, electrical condenser, photo-sensor such as chip carrier and pin grid arrays.In addition, also can use in the container class that microwave oven is used.Composition of the present invention as the manufacturing resin combination of aforesaid circuit card, semi-conductor interlayer dielectric, antenna element, high frequency coaxial cable insulating material etc., is useful especially.

These electronic components can utilize well-known method to make.For example, printed circuit board (PCB) can be tabular by composition of the present invention is configured as, then utilize on its surface as required metallic membranes such as formation copper such as plating operation, make circuit according to ordinary method and obtain.

The shaping of the present composition also can wait according to well-known manufacturing process, for example injection moulding, extrusion moulding, compressed moulding, casting molding and carry out.

In addition, according to the present invention, by with nano-scale carbon tube, particularly above-mentioned 2 or 3 a described nano-scale carbon tube, be added on the electronic component that the resin combination of the present invention that forms in the resin obtains with the minute quantity of 0.0001～0.4 weight %, in GHz band, can make dielectric loss angle tangent (tan δ) and reduce when using resin separately or the rising of tan δ when suppressing to use resin separately.

Thereby, the invention provides the tan δ of electronic component in the GHz band or the method for inhibition tan δ rising that a kind of reduction is obtained by resin, described resin is from by aforementioned thermoplastic resin, at least a resin of selecting in the group that compound resin constituted of curable resin and thermoplastic resin and curable resin, this method feature is, with respect to from by aforementioned thermoplastic resin, at least a resin of selecting in the group that compound resin constituted of curable resin and thermoplastic resin and curable resin, with the ratio of 0.0001～0.4 weight % with nano-scale carbon tube, a particularly above-mentioned item 2 or 3 a described nano-scale carbon tube are added in the resin.

Equally, the present invention also provide nano-scale carbon tube, particularly above-mentioned 2 or 3 a described nano-scale carbon tube be used for reducing the electronic component made by at least a resin of the group that compound resin constituted that is selected from aforementioned thermoplastic resin, curable resin and thermoplastic resin and curable resin in the GHz band tan δ or suppress application in the rising of tan δ.

And, according to the present invention, by with nano-scale carbon tube, particularly above-mentioned 2 or 3 a described nano-scale carbon tube, be added on the electronic component that the resin combination of the present invention that forms in the resin is made with 0.0001～0.4 weight % minute quantity, in the GHz band, can make dielectric loss angle tangent (tan δ) and reduce when separately using resin or the rising of tan δ when suppressing to use resin separately, on the other hand, physicalies such as the original specific inductivity of resin, thermotolerance, physical strength do not change in fact and remain stationary.

Thereby, the invention provides a kind of making by from aforementioned thermoplastic resin, the tan δ of the electronic unit that at least a resin of selecting in the group that the compound resin of curable resin and thermoplastic resin and curable resin constituted obtains in GHz band reduces when using resin separately or suppresses its rising, keep the original specific inductivity of resin, thermotolerance, physical strength (for example: tensile strength, the extension at break degree, hardness etc.), rerum naturas such as chemical property, the method of dielectric characteristics particularly, it is characterized in that, with respect to described resin, with the ratio of 0.0001～0.4 weight % with nano-scale carbon tube, a particularly above-mentioned item 2 or 3 a described nano-scale carbon tube are added in the resin.

Equally, the present invention also provide nano-scale carbon tube, particularly above-mentioned 2 or 3 a described nano-scale carbon tube be used for making the tan δ of electronic component in the GHz band that make by at least a resin of the group that compound resin constituted that is selected from aforementioned thermoplastic resin, curable resin and thermoplastic resin and curable resin than resin original tan δ reduce or suppress the tan δ of this electronic component in the GHz band rising, keep the application in original other characteristic of resin.

Embodiment

Below, exemplify reference example (Production Example of nano-scale carbon tube), embodiment and comparative example, the present invention will be described in more detail, but the present invention is not limited to these embodiment, and various changes can be arranged.

Reference example 1

The manufacturing of amorphous nano-scale carbon tube

Amorphous nano-scale carbon tube is made with method as follows.

On the PTFE film of 60 μ m * 10mm * 10mm, after anhydrous chlorides of rase iron powder (particle diameter 500 μ m following) 10mg sprinkled equably, carry out excitation of plasma.The condition of excitation of plasma is as described below:

Atmosphere: argon gas (Ar)

The interior pressure: 0.01 holder

Power input: 300W

RF frequency: 13.56MHz.

After reaction finishes, utilize scanning electron microscope (SEM) and X-ray diffraction to confirm to have formed amorphous nano-scale carbon tube (external diameter: 10～60nm; Length: 5～6 μ m).

In addition, the X-ray diffraction angle of the amorphous nano-scale carbon tube that obtains (2 θ) is 19.1 degree, and the carbon net plane that calculates thus interval (d002) is

The half breadth of 2 θ is 8.1 degree.

Reference example 2

By making raw material with toluene, making catalyzer, open 2002-338220 number described method according to the spy and react, obtain comprising that iron carbide partly is included in the carbonaceous material of the iron-carbon complex of spatial portion in the pipe of nano-sheet carbon pipe with iron(ic) chloride.

The result who observes from SEM as can be known, the iron that obtains-carbon complex external diameter is that 20～100nm, length are 1～10 micron, and is linear high.In addition, the thickness of the wall portion that is made of carbon is 5～40nm, comes down in length range uniformly.This wall portion, in tem observation, can see, its carbon wall is not nested shape or reel, but piece shape (so-called paper mache shape or papier-mache shape) together, in addition, confirm that by X-ray diffraction method it is that the mean distance (d002) that has between the carbon wire side is the nano-sheet carbon pipe of the following graphite matter structure of 0.34nm.In addition, confirm by X-ray diffraction, EDX, spatial portion in the pipe of the nano-sheet carbon pipe of the iron-carbon complex that constitutes the invention described above, iron carbide is partially filled.

With Electronic Speculum (TEM) when observing, the filling ratio that is mixed with the iron carbide of filling in the tube space portion at nano-sheet carbon pipe (i.e. the space that is surrounded by the tube wall of nano-sheet carbon pipe) is the iron-carbon complex of the various filling ratios in 20～60% the scope with the carbonaceous material that includes a plurality of iron-carbon complexes that constitute carbonaceous material of the present invention that obtains.

A plurality of visuals field of tem observation picture that will the iron carbide that spatial portion is filled in the pipe of the nano-sheet carbon pipe of these a plurality of iron-carbon complexes are observed, and the mean cut-off rate of calculating is 30%.In addition, the R value of being calculated by X-ray diffraction is 0.57.

Reference example 3

Iron-carbon complex (part comprises the nano-sheet carbon pipe of iron carbide) 1g with above-mentioned reference example 2 obtains is scattered among the hydrochloric acid 100ml of 1N, handles 6 hours in stirring at room, and carries out filtering separation.Further the hydrochloric acid 100ml with 1N handles 2 times equally, obtains the nano-sheet carbon pipe of hollow.

The nano-sheet carbon pipe that obtains is compared with the iron-carbon complex of above-mentioned reference example 2, and the thickness of shape, profile, length, wall portion comes down to identical.In addition, in tem observation, can see, the carbon wall of this wall portion, not that nested shape neither reel, but piece shape (so-called paper mache shape or papier-mache shape) together, in addition, confirm that it is that the mean distance (d002) that has between the carbon wire side is the nano-sheet carbon pipe of the following graphite matter structure of 0.34nm by X-ray diffraction method.

Embodiment 1～5

Usability photosensitiveness acrylic resin (material that epoxy acrylate resin (Japanese chemical drug society system EAM-2160) 98g, Photoepolymerizationinitiater initiater (the Japanese chemical drug system DETX-S of society) 1g, photopolymerization promoter (the Japanese chemical drug system EPA of society) 1g are mixed) is as curable resin.

Use iron-carbon complex that reference example 2 obtains as nano-scale carbon tube in the described ratio of table 1.Shown in the table 1 is use level (weight part) with respect to the nano-scale carbon tube of total amount 100 weight parts of above-mentioned epoxy group(ing) acrylic resin, Photoepolymerizationinitiater initiater, photopolymerization promoter.

Utilize ceramic 3 rollers mill (ノ リ Network ケ カ Application パ ニ one system NR-42A) to mix resin and nano-scale carbon tube (iron-carbon complex), obtain making nano-scale carbon tube to be dispersed in mashed prod in the resin.

The mashed prod that obtains is packed in the columnar mould with mercuryvapour lamp (500W) irradiation ultraviolet radiation (illuminated line amount: 6J/cm ²), obtain columnar molding.The central part cutter of this molding is worn, obtained estimating and use sample.As Fig. 5 501 shown in, this evaluation sample is coaxial shape machining object, makes the annular shape, its external diameter (2b) be 0.7cm, internal diameter (2a) for 0.3cm, highly (L) be 0.15cm.

Comparative example 1～3

The total amount that the usage quantity of iron-carbon complex is set at respect to above-mentioned epoxy group(ing) acrylic resin, Photoepolymerizationinitiater initiater, photopolymerization promoter is 0 weight %, 1.02 weight % or 2.98 weight %, in addition, all the other and embodiment 2 operate equally, obtain being used for the evaluation sample of comparison.

Embodiment 6

Substitute iron-carbon complex, the amorphous nano-scale carbon tube that uses reference example 1 to obtain, in addition, all the other and embodiment 2 operate equally, obtain estimating using sample.

Comparative example 4 and 5

The total amount that the usage quantity of amorphous nano-scale carbon tube is set at respect to above-mentioned epoxy group(ing) acrylic resin, Photoepolymerizationinitiater initiater, photopolymerization promoter is 1.19 weight % or 3.02 weight %, in addition, all the other and embodiment 6 operate equally, obtain being used for the evaluation sample of comparison.

Embodiment 7

Substitute iron-carbon complex, use commercially available single-layer carbon nano-tube in the described ratio of table 1, in addition, all the other and embodiment 1-5 operate equally, obtain estimating and use sample.

Comparative example 6～8

Being set at the amount of single-layer carbon nano-tube with respect to above-mentioned photosensitivity acrylic resin (material that epoxy group(ing) acrylic resin (the Japanese chemical drug system EAM-2160 of society) 98g, Photoepolymerizationinitiater initiater (the Japanese chemical drug system DETX-S of society) 1g, photopolymerization promoter (the Japanese chemical drug system EPA of society) 1g are mixed) is 0.50 weight %, 0.98 weight %, 3.01 weight %, in addition, all the other and embodiment 7 operate equally, obtain being used for the evaluation sample of comparison.

Table 1

Test example 1

The evaluation sample that obtains for previous embodiment 1-7 and comparative example 1-8, according to black river realize etc., Kyoto Prefecture medium-sized and small enterprises integrating center technical intelligence, 2002, the described method of No.30, measure tan δ and specific inductivity in the GHz band.

That is, utilize following method to carry out: the evaluation of coaxial shape of coaxial connector that will be processed into the APC7mm specification is with sample (external diameter (2b): 0.7cm, internal diameter (2a): 0.3cm, highly (L): 0.15cm) insert in as shown in Figure 5 the outer conductor 503, by measuring S ₁₁, S ₂₁Two S parameters are obtained complex permittivity.Utilize following method to carry out during mensuration: to utilize the vector network analyzer, insert the determined material of the coaxial shape of the coaxial connector that is processed into the APC7mm specification, by measuring S ₁₁, S ₂₁Two S parameters are obtained complex permittivity.

The measurement result of the tan δ of the evaluation usefulness sample that comparative example 1, embodiment 2, embodiment 3 and comparative example 3 obtain as shown in Figure 6.The evaluation that obtains of comparative example 1, embodiment 2 and embodiment 3 with the measurement result of the specific inductivity of sample as shown in Figure 7 in addition.By Fig. 6 and Fig. 7 as can be known, compare with sample (comparative example 1) with the evaluation that obtains by resin separately that does not contain iron-carbon complex, the evaluation that is obtained by the resin combination of the iron-carbon complex that contains specified quantitative is with sample (embodiment 2 and 3), the rising of dielectric loss angle tangent (tan δ) is inhibited, and specific inductivity does not change in fact.

The measurement result of the tan δ of the evaluation usefulness sample that comparative example 1, embodiment 6 and comparative example 4 obtain as shown in Figure 8.As shown in Figure 8, the evaluation sample that contains the embodiment 6 of the 0.01 weight % amorphous nano-scale carbon tube of having an appointment, with the evaluation that constitutes by resin separately with sample (comparative example 1) or contain above the evaluation of the amorphous nano-scale carbon tube of 1 weight % and compare with sample (comparative example 4), the rising of tan δ is inhibited.

In addition, the evaluation that obtains of comparative example 1 and embodiment 7 with the measurement result of the tan δ of sample as shown in Figure 9.As shown in Figure 9, contain the evaluation sample of the embodiment 7 of the 0.02 weight % carbon nanotube of having an appointment, compare with sample (comparative example 1) with the evaluation that is made of resin separately, the rising of tan δ is inhibited.

In addition, the evaluation that is obtained by each embodiment and comparative example is as shown in table 2 with tan δ and the measurement result of specific inductivity of sample in 1GHz, 5GHz and 10GHz.

Table 2

By above-mentioned table 2 as can be known, the electronic component that obtains with the resin combination of the present invention that contains the specified quantitative nano-scale carbon tube, in the range of frequency of GHz band, particularly 1～10GHz, compare with the electronic component that obtains by the resin that does not contain nano-scale carbon tube (comparative example 1), the rising of tan δ is inhibited, and resin original physical properties (specific inductivity) does not almost have deterioration, remains unchanged substantially.

Test example 2

For molding (tension test sheet) to obtain with the same mode of comparative example 1,2 and embodiment 1～5, measure tensile strength according to JIS K6911, measure the extension at break degree according to JIS C2151, measure pencil hardness according to JIS K5600.The tension test sheet of the mensuration usefulness of these physicalies, based on these JIS standards for being prepared.

The result is as shown in table 3.As shown in Table 3, compare with the above-mentioned physics value (the original physics value of resin) of the comparative example 1 that does not contain nano-scale carbon tube, the above-mentioned physics value of molding that contains the comparative example 2 of the nano-scale carbon tube that surpasses addition scope of the present invention changes, and can think considerable change; Relative therewith, contain the above-mentioned physics value of molding of the embodiment 1～5 of the nano-scale carbon tube in the addition scope of the present invention, compare with the physics value (the original physics value of resin) of comparative example 1 big variation does not take place, not notable difference.

Table 3

	Tensile strength ( *1) (MPa)	The extension at break degree ( *2) (％)	Pencil hardness ( *3)
				Comparative example 1	45	2.5	5H
Embodiment 1	47	2.3	5H
				Embodiment 2	50	2.4	5H
Embodiment 3	46	2.5	5H
				Embodiment 4	50	2.2	5H
Embodiment 5	52	2.0	5H
				Comparative example 2	55	1.9	6H

Remarks: test method

( ^*1) ：JIS K6911

( ^＊2)：JIS C2151

( ^*3) ：JIS K5600

Embodiment 8～11

Usability photosensitiveness acrylic resin (material that epoxy acrylate resin (Japanese chemical drug society system EAM-2160) 98g, Photoepolymerizationinitiater initiater (the Japanese chemical drug system DETX-S of society) 1g, photopolymerization promoter (the Japanese chemical drug system EPA of society) 1g are mixed) is as resin.

Use iron-carbon complex that reference example 2 obtains as nano-scale carbon tube in the described ratio of following table 4.In table, listed the use level (weight part) of nano-scale carbon tube with respect to above-mentioned photosensitivity acrylic resin (total amount of epoxy acrylate resin, Photoepolymerizationinitiater initiater, photopolymerization promoter) 100 weight parts.

At first, utilize ceramic 3 rollers mill (ノ リ Network ケ カ Application パ ニ one system NR-42A) to mix resin and nano-scale carbon tube (iron-carbon complex), nano-scale carbon tube is dispersed in the resin, obtain the mashed prod of embodiment 8.

Then, mashed prod with the above-mentioned embodiment that obtains 8, with the mashed prod of comparative example 1 (composition that constitutes by epoxy acrylate resin, Photoepolymerizationinitiater initiater and photopolymerization promoter) dilution, so that it becomes the composition of following table 4, obtain the mashed prod of the embodiment 9～11 lower than embodiment 8 nano-scale carbon tube concentration.

The mashed prod that obtains is packed in the columnar mould with mercuryvapour lamp (500W) irradiation ultraviolet radiation (illuminated line amount: 6J/cm ²), obtain columnar molding.The central part cutter of this molding is worn, obtained estimating and use sample.This evaluation sample is coaxial shape machining object, makes ring-like shape, its external diameter be 0.7cm, internal diameter be 0.3cm, highly for 0.3cm.

Test example 3

The evaluation sample that uses previous embodiment 8～11 to obtain, in addition, all the other and test example 1 are operated equally, are determined at the tan δ in the GHz band.

The measurement result of the tan δ of the evaluation usefulness sample that embodiment 8～11 obtains as shown in figure 10.

As shown in Figure 10, compare with sample (comparative example 1) with the evaluation that obtains by resin separately that does not contain iron-carbon complex, by the evaluation sample that the resin combination of the iron-carbon complex that contains specified quantitative obtains, the rising of dielectric loss angle tangent (tan δ) is inhibited.

In addition, the evaluation that obtains of embodiment 8～11 is as shown in table 4 with the measurement result of the tan δ of sample in 1GHz, 5GHz and 10GHz.

Table 4

Embodiment 12

Substitute amorphous nano-scale carbon tube, the nano-sheet carbon pipe that uses reference example 3 to obtain, in addition, all the other and embodiment 6 operate equally, obtain estimating using sample.

With with the same method of test example 1, measure the evaluation that obtains with tan δ and the specific inductivity of sample in the GHz band, its result, tan δ and specific inductivity are all identical in fact with embodiment 6.

Embodiment 13～17

(Dyhard RU 100: the system DICY7 of ジ ヤ パ Application エ Port キ シ レ ジ Application Co., Ltd.) thermosetting epoxy resin that mixes of 2g is as resin with brominated bisphenol a type epoxy resin (ジ ヤ パ Application エ Port キ シ レ ジ Application Co., Ltd. system, trade(brand)name " 5046B80 ") 98g, solidifying agent in use.

Use iron-carbon complex that reference example 2 obtains as nano-scale carbon tube in the described ratio of table 5.

In the table 5, listed the use level (weight part) of nano-scale carbon tube with respect to above-mentioned thermosetting epoxy resin 100 weight parts.

Utilize ceramic 3 rollers mill (ノ リ Network ケ カ Application パ ニ one system NR-42A) to mix resin and nano-scale carbon tube (iron-carbon complex), nano-scale carbon tube is dispersed in the resin, obtain mashed prod.

The mashed prod that obtains is packed in the columnar mould, make it, obtain columnar molding 220 ℃ of thermofixations 30 minutes.The central part cutter of this molding is worn, obtained estimating and use sample.This estimate with sample as Fig. 5 501 shown in, be coaxial shape machining object, make ring-like shape, its external diameter (2b) be 0.7cm, internal diameter (2a) for 0.3cm, highly (L) be 0.15cm.

Comparative example 9～11

Being set at the usage quantity of iron-carbon complex with respect to above-mentioned thermosetting epoxy resin is 0 weight %, 1.05 weight % or 3.02 weight %, and in addition, all the other and embodiment 13～17 operate equally, obtain being used for the evaluation sample of comparison.

Embodiment 18 and 19

Substitute iron-carbon complex, by the amorphous nano-scale carbon tube that the described amount of table 5 uses reference example 1 to obtain, in addition, all the other and embodiment 13～17 operate equally, obtain estimating and use sample.

Comparative example 12

Being set at the usage quantity of amorphous nano-scale carbon tube with respect to above-mentioned thermosetting epoxy resin is 3.02 weight %, and in addition, all the other and embodiment 18 operate equally, obtain being used for the evaluation sample of comparison.

Test example 4

The evaluation sample that uses previous embodiment 13～19 and comparative example 9～12 to obtain, in addition, all the other and test example 1 are operated equally, are determined at the tan δ in the GHz band.The result is as shown in table 5.

Table 5

As shown in Table 5, compare with sample (comparative example 9) with the evaluation that obtains by resin separately that does not contain iron-carbon complex, by the evaluation sample that the resin combination that contains the iron-carbon complex of specified quantitative according to the present invention obtains, the rising of dielectric loss angle tangent (tan δ) is inhibited.

Embodiment 20～23

In Japanese Port リ ケ system Co., Ltd. system high-pressure process new LDPE (film grade) (LDPE), add as thermoplastic resin 1 weight % nano-scale carbon tube, be iron-carbon complex that the amorphous nano-scale carbon tube that obtains of reference example 1 or reference example 2 obtain, and utilize pressurization both arms type kneader (gloomy mountain making institute of Co., Ltd.) to heat and mix.

In the thing that mixes of the nano-scale carbon tube that contains 1 weight % that so obtains, append LDPE, so that the content of nano-scale carbon tube becomes the described ratio of table 6, utilizing pressurization both arms type kneader to heat mixes, then, utilize the injection machine of Nissei Plastic Industrial Co., Ltd's system, make the bar-shaped evaluation test sheet of diameter 3mm, long 120mm.

For the evaluation test sheet that so obtains, according to the described method of document (Mitsubishi's electric wire Times in April, 2003 " high frequency concentric cable with the exploitation of low loss material "-ultra-high frequency zone (GHz band) utilize rhumbatron method of perturbation evaluation dielectric characteristics-described in method), utilize the rhumbatron method of perturbation, be determined at the dielectric loss angle tangent among the 2GHz.

The result is as shown in table 6.Listed the use level (weight part) of nano-scale carbon tube in the table 6 with respect to above-mentioned thermoplastic resin 100 weight parts.

Comparative example 13

Do not use nano-scale carbon tube, in addition, all the other and embodiment 20～23 operate equally, obtain being used for the bar-shaped evaluation test sheet of comparison, measure dielectric loss angle tangent.The result is as shown in table 6.

Table 6

As shown in Table 6, compare with the bar-shaped evaluation test sheet (comparative example 13) that obtains by the resin combination that does not contain nano-scale carbon tube, the tan δ of the bar-shaped evaluation test sheet (embodiment 20～23) that is obtained by the resin combination that contains the nano-scale carbon tube of specified quantitative according to the present invention reduces in 2GHz.

Industrial applicibility

According to the present invention, the electronic component that is obtained by the resin combination that in resin, adds above-mentioned nano-scale carbon tube with the minute quantity of 0.0001～0.4 % by weight and form, in the GHz band, dielectric loss angle tangent (tan δ) ratio reduces when using resin separately, the rising of tan δ in the time of maybe can suppressing to use resin separately, in addition, the drift that also can suppress the tan δ that the frequency by GHz causes changes, on the other hand, the original dielectric constant of resin, heat resistance, mechanical strength are (for example, tensile strength, extension at break degree, hardness etc.), substantial variation do not occur, and remains unchanged in physical property, the particularly dielectric property such as chemical characteristic.

Thereby, by using such resin combination, provide circuit board material, particularly the GHz band that can be suitable for electric, the electronic equipment electronic component with circuit board material etc.

Claims (14)

1. charged sub-element resin combination of GHz, it is characterized in that, contain at least a resin and the nano-scale carbon tube that are selected from the group that the compound resin by thermoplastic resin, curable resin and thermoplastic resin and curable resin constitutes, containing of nano-scale carbon tube is proportional, with described resin is benchmark, be 0.0001～0.4 weight %

Wherein said carbon nanotube is:

(ii) amorphous nano-scale carbon tube;

(iii) nano-sheet carbon pipe;

(iv) by (a) be selected from the group that the multilayer carbon nanotube by nano-sheet carbon pipe and nesting structure constitutes the carbon pipe and (b) iron carbide or iron constitute, and the pipe of this carbon pipe (a) in the iron-carbon complex of this iron carbide of existence or iron (b) in 10～90% the scope of spatial portion; Or

(v) (ii) above-mentioned～two or more mixture in (iv).

2. the charged sub-element resin combination of GHz as claimed in claim 1, wherein, nano-scale carbon tube is an amorphous nano-scale carbon tube, is in the X-ray diffraction method of CuK α in incident X-rays, utilizes the interplanar of the carbon net plane 002 of X-ray diffraction method mensuration to be divided into More than, diffraction angle 2 θ are below 25.1 degree, the half breadth of 2 θ band is more than 3.2 degree.

3. the charged sub-element resin combination of GHz as claimed in claim 1, wherein, resin is at least a thermoplastic resin that is selected from the group that is made of polyolefin resin, vibrin, polyamide resin, fluoro-resin, polystyrene resin, polyvinyl chloride (PVC) RESINS, methacrylate resin, acrylate resin, polycarbonate resin, polysulfone resin, polyethersulfone resin, polyphenylene sulfide, polyphenylene oxide resin, ABS resin, polyether-ether-ketone resin, thermoplastic polyimide resin, polyetherimide resin, polyacetal, polyarylester and polyethers nitrile resin.

4. the charged sub-element resin combination of GHz as claimed in claim 1, wherein, resin is at least a curable resin that is selected from the group that is made of thermosetting resin, light-cured resin and electrocuring resin.

5. the charged sub-element resin combination of GHz as claimed in claim 1, wherein, resin is to be selected from by the thermoplastic resin of the cured article that wherein is dispersed with curable resin and wherein to be dispersed with at least a compound resin in the group that the curable resin of thermoplastic resin constitutes.

6. the charged sub-element resin combination of GHz as claimed in claim 1, wherein, containing of nano-scale carbon tube is proportional, is benchmark with the resin, is 0.001～0.4 weight %.

7. the charged sub-element resin combination of GHz as claimed in claim 1, wherein, nano-scale carbon tube is described amorphous nano-scale carbon tube, its addition is 0.0001～0.1 weight % with respect to resin.

8. the charged sub-element resin combination of GHz as claimed in claim 1, wherein, nano-scale carbon tube is described iron-carbon complex, its addition is 0.0001～0.4 weight % with respect to resin.

9. the charged sub-element resin combination of GHz as claimed in claim 1, wherein, nano-scale carbon tube is described nano-sheet carbon pipe, its addition is 0.0001～0.1 weight % with respect to resin.

10. charged sub-element of GHz, it is obtained with resin combination by the charged sub-element of GHz as claimed in claim 1.

11. the charged sub-element of GHz as claimed in claim 10, it is circuit card, semi-conductor interlayer dielectric, antenna element or high frequency coaxial cable insulating material.

12. the charged sub-element of GHz as claimed in claim 10, wherein, the tan δ of resin combination is reduced to below 0.1 in the GHz band, and resin keeps original other physicals.

13. one kind reduce electronic component in GHz band tan δ or be suppressed at the method that the tan δ in the GHz band rises, described electronic component is obtained by at least a resin that is selected from by in the group that compound resin constituted of thermoplastic resin, curable resin and thermoplastic resin and curable resin, the method is characterized in that, in this resin being that the ratio of 0.0001～0.4 weight % is added nano-scale carbon tube with respect to this resin

Wherein said carbon nanotube is:

(ii) amorphous nano-scale carbon tube;

(iii) nano-sheet carbon pipe;

(iv) by (a) be selected from the group that the multilayer carbon nanotube by nano-sheet carbon pipe and nesting structure constitutes the carbon pipe and (b) iron carbide or iron constitute, and the pipe of this carbon pipe (a) in the iron-carbon complex of this iron carbide of existence or iron (b) in 10～90% the scope of spatial portion; Or

(v) (ii) above-mentioned～two or more mixture in (iv).

14. reduce when a ratio uses resin separately the electronic component that obtains by this resin in the GHz band tan δ or suppress the method that it rises and keeps original other physicals of this resin, this resin is at least a resin that is selected from by in the group that compound resin constituted of thermoplastic resin, curable resin and thermoplastic resin and curable resin, the method is characterized in that, in this resin being that 0.0001～0.4 weight % ratio is added nano-scale carbon tube with respect to this resin

Wherein said carbon nanotube is:

(ii) amorphous nano-scale carbon tube;

(iii) nano-sheet carbon pipe;

(iv) by (a) be selected from the group that the multilayer carbon nanotube by nano-sheet carbon pipe and nesting structure constitutes the carbon pipe and (b) iron carbide or iron constitute, and the pipe of this carbon pipe (a) in the iron-carbon complex of this iron carbide of existence or iron (b) in 10～90% the scope of spatial portion; Or

(v) (ii) above-mentioned～two or more mixture in (iv).

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