CN100416710C - Carbon oil for producing carbon impedance, its production and carbon impedance component - Google Patents
Carbon oil for producing carbon impedance, its production and carbon impedance component Download PDFInfo
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- CN100416710C CN100416710C CNB2004100960587A CN200410096058A CN100416710C CN 100416710 C CN100416710 C CN 100416710C CN B2004100960587 A CNB2004100960587 A CN B2004100960587A CN 200410096058 A CN200410096058 A CN 200410096058A CN 100416710 C CN100416710 C CN 100416710C
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Abstract
The present invention relates to carbon oil for producing carbon impedance, a production method thereof and a carbon impedance component, which belongs to the technical field of resistors. The carbon oil for producing carbon impedance comprises carbon black, resin connection materials, a cross-linking agent and solvents. The present invention is characterized in that the carbon black is dual-component carbon black; the selection of the dual-component carbon black meets one of the conditions: the absolute value of d1-d2 is more than 4 nm; the absolute value of A1-A2 is more than 50 cc/ 100g, wherein d1 and d2 are respectively the average particle diameters of the two kinds of the carbon black; A1 and A 2 are respectively the DBP value corresponding to the two kinds of the carbon black. The present invention has the advantages of simple manufacturing process for making the carbon oil, and narrow range of the distribution of the square impedance for making the carbon impedance component. The present invention overcomes the defects of pinholes in end products of the carbon impedance component, cracks, etc. The properties of the carbon impedance component and the stability of the impendence value of the products are enhanced.
Description
Technical field
The invention belongs to the resistor technical field, the carbon resistance component that relates to a kind of carbon oil that is used to manufacture carbon resistance component and preparation method thereof and use this carbon oil to manufacture.
Background technology
The preparation method of traditional carbon resistance component comprises: a certain amount of conductive carbon black is scattered in to be modulated into pastel in the solution of thermosetting resin be carbon oil, subsequently carbon oil is formed the pattern of definite shape and size on the surface of rigidity printed wire board substrates such as FR1, FR2, FR4 by screen print means etc., heat solvent evaporation at last and further be heated under 100～180 ℃ resin is cured, thereby form carbon resistance component.
Generally speaking, increase along with carbon black content in the carbon oil, the conductivity of system increases, and resistance value descends, but milder in the initial period changes in resistance, when the content of carbon black is increased to certain value, when promptly reaching so-called " threshold values is oozed in the Chongqing ", because the formation conductive network is oozed in the Chongqing of carbon black in system, the resistance of system significantly descends, that is to say ooze threshold values in the Chongqing near, significant variation will take place because of the minor variations of carbon black content in the system in the resistance of system; Further increase the content of carbon black, the decline of resistance value will tend towards stability again.
So for the system of single conductive filler (carbon black), because resistance change is too fast near " threshold values is oozed in the Chongqing ", so the very difficult adjustment of resistance value, that is to say that being difficult to obtain the carbon black Chongqing oozes the carbon oil product of the interior pairing side's resistance of threshold values scope.
In order to obtain the carbon oil product with certain Standard resistance range, traditional method is the carbon oil product that modulates a series of different side's resistances by the kind of selecting conductive carbon black and the addition of controlling conductive carbon black, such as: 40 ohm-sq/25 μ m ± 10%; 400 ohm-sq/25 μ m ± 10%; 4000 ohm-sq/25 μ m ± 10%; 40000 ohm-sq/25 μ m ± 10%; 400000 ohm-sq/25 μ m ± 10%;＞2 * 10
9Ohm-sq/25 μ m ± 10% (promptly＞2million K Ω).Require to calculate the square resistance of required carbon oil product according to the size of carbon resistance component and resistance, a with that approaching with it of square resistance in the carbon oil series of products according to this side's resistance subsequently is main component, come with it then and immediate up and down that aly carries out a certain proportion of mixing, reach the carbon oil that demanding party of institute resistance requires thereby modulate.Such as need the side's of modulating resistance be the carbon oil of 300 ohm-sq/25 μ m ± 10%, then the side's of selection resistance is that the carbon oil of 400 ohm-sq/25 μ m ± 10% is a main component, by itself and square resistance is thereby that the carbon oil product of 40 ohm-sq/25 μ m ± 10% mixes the carbon oil that modulates demanding party of institute resistance with certain proportion, need add experiment to the ratio of two kinds of carbon oils is so on the one hand determined, technology is loaded down with trivial details relatively, on the other hand because the homogeneity question that mixes, the Standard resistance range that mixes the back carbon oil broadens, such as by original ± 10% become ± 20% or wideer, the bubble of introducing in this external mixed process will form pin hole in final carbon resistance component, defectives such as crackle, thus the performance of product and the stability of product resistance destroyed.That is to say that the problem that prior art exists is: preparation technology is more loaded down with trivial details, because the uniformity of mixing causes the resistance distribution broad of formed carbon resistance component and the bubble introduced in mixed process will be introduced defectives such as pin hole, crackle in final products, destroys the performance of carbon resistance component and the stability of product resistance.
Summary of the invention:
At the problems referred to above, the objective of the invention is to provide a kind of carbon resistance component that two kinds of different carbon blacks of conductivity are scattered in carbon oil among the thermoplastic resin solution and preparation method thereof and use this carbon oil to manufacture that contains, according to the present invention, the resistance of carbon oil is easy to adjust, do not need two kinds of carbon oils are mixed the resistance of adjusting carbon oil, and make the carbon resistance component produced have and advantages such as matrix good bonding force, narrow, the apparent complete shape and appearance of Standard resistance range, resistance are stable.
The inventor finds, when when the content of the conductive carbon black of key component is near its " threshold values is oozed in the Chongqing " scope, by adding the conductive filler of the different carbon black of conductivity as accessory constituent, can realize formed conductive network in the system is carried out " modification ", promptly the conductivity of conductive network number and conductive network is carried out autotelic control, even thereby the content of conductive filler is in its " threshold values is oozed in the Chongqing " scope, the square resistance of carbon oil is much slower than the variation of using single conductive filler time side resistance with the variation of conductive filler content, so just can realize the control to the square resistance of carbon oil easily and effectively.Based on this discovery, the present invention is accomplished.
Described DBP value is an oil factor, be the structural a kind of characterization technique of carbon black, its characterizing method is: drip repefral (DBP) in carbon black, till the viscosity of mixture changes suddenly, this moment the DBP that the 100g carbon black is dripped volume, be the DBP value.The conductivity of carbon black and the particle diameter of carbon black and structural relevant, particle diameter is more little, and conductivity is high more; Structural high more, conductivity is also high more.
According to the present invention, a kind of carbon oil that is used to manufacture carbon resistance component is provided, it comprises carbon black, resin binder, crosslinking agent and solvent, it is characterized in that described carbon black adopts bi-component carbon black system, and the selection of described bi-component carbon black one of meets the following conditions:
1) .|d
1-d
2|＞4nm; Or
2).|A
1-A
2|＞50cc/100g；
Wherein: d
1, d
2Be respectively the average grain diameter of two kinds of carbon blacks, A
1, A
2Be respectively the DBP value of two kinds of carbon blacks of correspondence.
As a kind of execution mode wherein, the selection of described bi-component carbon black can meet the following conditions simultaneously:
1) .|d
1-d
2|＞4nm; With
2).|A
1-A
2|＞50cc/100g；
Its precondition is: its DBP value of the carbon black component that wherein average grain diameter is little is also big.
The kind of described carbon black can be a carbon black commonly used when making the carbon oil of carbon resistance component in this area, and the present invention has no particular limits it, for example can be acetylene carbon black, oven process carbon black, thermal cracking carbon black, channel carbon black or their mixture.The average grain diameter of described carbon black can be adjusted respectively in the scope of 10～100nm, and the DBP value of described carbon black can be adjusted respectively in the scope of 50～250cc/100g.
In carbon oil according to the present invention, the content of described carbon black, resin binder, crosslinking agent and solvent can for:
Carbon black: 20～200 weight portions,
Resin binder: 100 weight portions,
Crosslinking agent: 5～25 weight portions and
Solvent: 200～1000 weight portions.
In carbon oil according to the present invention, in described bi-component carbon black, selecting the approaching wherein a kind of carbon black of conductance and the desired side's resistance of described carbon oil is the key component carbon black, be used to regulate the another kind of carbon black of carbon oil side's resistance accordingly as the accessory constituent carbon black, wherein the consumption of key component carbon black accounts for 70～95 weight % of total carbon black consumption, preferred 80～90 weight %; The consumption of corresponding accessory constituent carbon black accounts for 5～30 weight % of total carbon black consumption, preferred 10～20 weight %.
In the present invention, described resin binder has no particular limits, can adopt this area thermoplastic resin with caoutchouc elasticity commonly used in the prior art, mainly comprise polyvinyl butyral resin (PVB), polyvinyl ether resin, poly-IVE, PAUR and polyether-type ammonia ester etc., wherein polyvinyl butyral resin preferably.Polyvinyl butyral resin is the condensed products of polyvinyl alcohol and butyraldehyde compound, contain vinylacetate in its molecular structure, functional group such as vinyl alcohol and vinyl butyral, its performance characteristics is the transparency height, flexibility, flexibility is good, impact strength height under the low temperature, to resin, glass, metal have good adhesive property and and phenolic aldehyde, urea aldehyde, the compatibility that resins such as epoxy are good, thereby give corresponding carbon oil product and matrix good bonding force, the corresponding good advantages such as compliance of carbon resistance component, the making of carbon resistance component on the making of especially suitable thick film resistance element and the flexible circuit board.
Adding crosslinking agent is intensity, hardness and the resistance to wear that improves the adhesive property and the corresponding carbon resistance component of carbon oil for further.In the present invention, the kind of described crosslinking agent has no particular limits, can adopt this area crosslinking agent commonly used in the prior art, for example can be epoxy resin, epoxy-phenolic resin, phenolic resins, Lauxite, melamine resin, unsaturated polyester resin, alkyd resins etc.Consider and the compatibility of polyvinyl butyral resin that phenolic resins, epoxy resin and melamine resin are preferable selection.With respect to the resin binder of 100 weight portions, the consumption of described crosslinking agent is 5～25 weight portions, when being lower than 5 weight portions, crosslinking degree is low, and poor heat stability is when dosage of crosslinking agent surpasses 25 weight portions, crosslinking degree is too high, and carbon oil solidifies the bonding poor of back and matrix, is easy to generate and peels off.
In the present invention, described choice of Solvent has no particular limits, and can adopt this area solvent commonly used in the prior art.Usually, depend on the type of used resin binder and crosslinking agent for the selection of the type of solvent for use, common selected solvent is: such as the alcohols of methyl alcohol, ethanol, normal propyl alcohol, isopropyl alcohol; Such as acetone, ketone such as methyl ethyl ketone (2-butanone), methyl iso-butyl ketone (MIBK) and such as ester classes such as methyl acetate, ethyl acetate and ro-butyl acetate.Consider the solubility property of solvent and the volatile performance of solvent, select the mixing of one or several solvents of above-mentioned solvent usually.Consumption for solvent does not have strict restriction, and with respect to the resin binder of 100 weight portions, the consumption that needs solvent is 500～1000 weight portions usually.Resin may not fully dissolve when the consumption of solvent was lower than 500 weight portions, the consistency of quality that influence mixes and corresponding carbon oil; When the consumption of solvent surpassed 1000 weight portions on the other hand, the viscosity of system was low excessively, will influence the processability of carbon oil.The range of viscosities of carbon oil be preferably 5000～20000mPas (measure test condition with the BROOKFIELD viscosimeter: 20 ℃ of temperature, stirring rod rotating speed be 20 the week/min).When viscosity was lower than 5000mPas, system mobile very good was difficult to guarantee the outward appearance and the size of product in the process of silk screen printing; When viscosity is higher than 20000mPas, in the process of frictioning, may damage, be easy on the other hand in the frictioning process, introduce bubble, produce defective web plate, thus the size of the carbon resistance component resistance that influence is prepared and stable.
In order to improve the dispersive property of carbon black in system, in carbon oil of the present invention, can also contain coupling agent, described coupling agent has no particular limits, for example can be titante coupling agent, as monoalkoxy type titanate coupling agent, monoalkoxy pyrophosphate type titanate coupling agent or huge legendary turtle mould assembly titanate coupling agent etc.; Also can be silane coupler, as amino vinylsilane coupling agent, methacryloxy silane coupler or epoxy silane coupling etc.With respect to the resin binder of 100 weight portions, the consumption of this coupling agent can be 2～5% of a carbon black weight for 1～40 weight portion.
Can also add the carbon oil product that additives such as plasticizer, paraffin have the excellent comprehensive performance with acquisition in addition as required.Described plasticizer has no particular limits, can adopt this area plasticizer commonly used in the prior art, comprise: glycols, fatty acid, phosphoric acid ester and phthalate etc., consider stability and with the compatibility of PVB, preferred plasticizer is dibutyl phthalate (DBP).With respect to the resin binder of 100 weight portions, the consumption of above-mentioned additive is 5～20 weight portions.
According to the present invention, a kind of preparation method of carbon oil also is provided, may further comprise the steps:
(1) the square resistance required according to described carbon oil, selecting the approaching wherein a kind of carbon black of conductivity and the desired side's resistance of described carbon oil is the key component carbon black, the another kind of carbon black of square resistance that is used to regulate carbon oil accordingly is as the accessory constituent carbon black, then two kinds of carbon blacks are mixed, wherein the consumption of key component carbon black accounts for 70～95 weight % of total carbon black consumption, the consumption of corresponding accessory constituent carbon black accounts for 5～30 weight % of total carbon black consumption, and the selection of described two kinds of carbon blacks one of meets the following conditions:
1) .|d
1-d
2|＞4nm; Or
2).|A
1-A
2|＞50cc/100g；
Wherein: d
1, d
2Be respectively the average grain diameter of two kinds of carbon blacks, A
1, A
2Be respectively the DBP value of two kinds of carbon blacks of correspondence;
(2) described carbon black is mixed with the thermoplastic resin solution who is formed by resin binder and solvent;
(3) in step (2) gained mixture, add crosslinking agent and mixing to form pastel.
The selection of wherein said two kinds of carbon blacks and the selection of other each composition no longer repeat at this as previously described.
In order to improve the dispersive property of carbon black in system, can select to use monoalkoxy type titanate coupling agent or titante coupling agents such as monoalkoxy pyrophosphate type titanate coupling agent or huge legendary turtle mould assembly titanate coupling agent that carbon black is carried out surface treatment, the condition of handling can be: at first with carbon black 100～200 ℃ of following vacuum bakeouts 6～24 hours, (concentration of solution has no particular limits with the toluene solution of carbon black and a certain amount of coupling agent subsequently, mainly be to determine according to the consumption of corresponding coupling agent) on high-speed mixer, mix, at last with solvent evaporation.Also can select silane coupler that carbon black is carried out surface treatment, the mode of processing can adopt dry method, is about to carbon black and silane coupler high-speed mixing and gets final product in 1～2 hour.The consumption of coupling agent can be 2～5% of carbon black weight.
The present invention also provides the carbon resistance component by foregoing carbon oil made of the present invention.
The method of being produced carbon resistance component by the carbon oil prepared according to the present invention can be that the carbon oil of preparation is prepared carbon resistance component by means such as silk screen printings; Detail can be: with the carbon oil that modulates, the mode of employing silk screen printing prepares the carbon resistance component of definite shape and size on pcb board, FPC or other matrixes.Mode of printing adopts by hand, manual semi-automatic screen process press all can; It is the monofilament polyester web plate of 61～90T or to use mesh be the stainless steel web plate of 77～100T that the silk screen web plate can adopt the net mould.Glue is scraped, and can to adopt Shore A hardness be 70～75 polyurethane scraper.The thickness of coating can be 0.5～15 μ m after dry and baking.
When threshold values is oozed in the content arrival Chongqing of carbon black, conductive carbon black oozes by the Chongqing and form conductive network in system, for single conductive carbon black system, increase along with carbon black content, conductive network grows out of nothing, from less to more, relatively poor to the control of the electric conductivity of conductive network and network density, thus show: controlled relatively poor on the square resistance of carbon oil product; And employing bi-component carbon black system, because both conductivity differ bigger, by kind and both consumptions of control of selecting carbon black, can realize that conductive phase destroys the formed conductive network of the high carbon black of conductivity to a certain extent relatively poor carbon black or weakens its conductivity, improves the square resistance of corresponding carbon oil product; Also can realize of the enhancing of the high carbon black of conductivity conversely, thereby improve its conductivity, reduce the square resistance of corresponding carbon oil product the relatively poor relatively formed conductive network of carbon black of conductivity.Controllability to the quantity of the conductivity of formed conductive network in the system and conductive network increases like this, and the controllability to carbon oil product side resistance also increases thereupon accordingly.In addition, the present invention is in the process of the carbon oil product of the certain Standard resistance range of preparation, the mixed process that does not relate to different side's resistance carbon oil products, thereby can realize preparing the carbon resistance component of resistance narrow distribution range on the one hand, the bubble of introducing in the carbon oil mixed process be can eliminate effectively and defectives such as the pin hole that in carbon resistance component, forms, crackle on the other hand, thereby the accuracy and the stability of the carbon resistance component resistance of preparation guaranteed.
The technology that the present invention prepares carbon oil is simple, the square resistance narrow distribution range of the carbon resistance component of making, there is not the problem of introducing bubble in the carbon oil mixed process, overcome defectives such as pin hole, crackle in the carbon resistance component final products, improved the performance of carbon resistance component and the stability of product resistance greatly.
Description of drawings
Fig. 1 is the process chart according to the preparation carbon resistance component of one embodiment of the present invention;
Fig. 2 is the structural representation of carbon resistance component;
SEM (scanning electron microscopy) photo of the carbon resistance component that Fig. 3 makes for embodiment 1;
The SEM photo of the carbon resistance component of the carbon oil correspondence that Fig. 4 makes for embodiment 4;
The SEM photo of the carbon resistance component of the carbon oil correspondence that Fig. 5 makes for embodiment 6;
The SEM photo of the carbon resistance component that Fig. 6 makes for comparative example 2.
Among the figure: 1-carbon oil layer, 2-wiring board
Embodiment
The following examples will be done further the present invention and specify, but these embodiment can not be interpreted as it is qualification to protection range of the present invention.
Embodiment 1
According to the process chart of preparation carbon resistance component shown in Figure 1, (average grain diameter is 30nm, and the DBP value is 174cc/100g, and the BET surface area is 254m to take by weighing the V-XC72 carbon black
2/ g) (average grain diameter is 29nm, and the DBP value is 102cc/100g, and the BET surface area is 84m with the BP460 carbon black
2/ g.) two kinds of carbon black 30 weight portions (both weight ratios are 3: 1,), vacuumize, after mixing by ball mill, the toluene solution (concentration of solution is 10 weight %) that adds 4% compound monoalkoxytitanates coupling agent (CT-136) of carbon black weight mixed 2 hours on high-speed mixer, then with solvent evaporation.With the gained mixture join by the polyvinyl butyral resin of 100 weight portions (
B-76) and in the solution formed of the methyl ethyl ketone of 500 weight portions and mix, then to the concentration that wherein adds 100 weight portions be 10 weight % phenolic resins (
EP560) methyl ethyl ketone solution is promptly prepared carbon oil product of the present invention after mixing.
Adopt above-mentioned carbon oil, print out as shown in Figure 2 carbon resistance component by manual silk screen printing on the rigidity wiring board, among the figure, 1 is carbon oil, and 2 is wiring board, after 150 ℃ baking 30min solidify down, its resistance is tested, and test result is listed in the table 2.The electron micrograph of the carbon resistance component surface texture that Fig. 3 prepares for present embodiment, as can be seen from Figure 3: the carbon resistance component surface of preparing is very regular, does not have blemish such as tangible crackle, pin hole.
Embodiment 2
(average grain diameter is 20nm, and the DBP value is 115cc/100g, and the BET surface area is 205m to take by weighing Conductex SC Ultra carbon black
2/ g) (average grain diameter is 45nm, and the DBP value is 121cc/100g, and the BET surface area is 42m with the BP280 carbon black
2/ g) two kinds of carbon black 60 weight portions (both weight ratios are 4: 1), vacuumize, after mixing by ball mill, the toluene solution that adds the compound monoalkoxytitanates coupling agent (CT-136) of 4 weight % mixed on high-speed mixer 2 hours, then with solvent evaporation (consumption of coupling agent be carbon black weight 2%).Joining the gained mixture in the solution of being made up of the ethanol of the PAUR (Luoyang Liming chemical Inst product) of 100 weight portions and 800 weight portions and mix, is 10% epoxy resin (Araldite then to the weight percent concentration that wherein adds 100 weight portions
TM6069) solution is promptly prepared carbon oil product of the present invention after mixing.
Adopt above-mentioned carbon oil, print out as shown in Figure 2 carbon resistance component by manual silk screen printing on the rigidity wiring board, after 150 ℃ baking 30min solidify down, its resistance is tested, test result is listed in the table 2.
Embodiment 3
(average grain diameter is 20nm, and the DBP value is 115cc/100g, and the BET surface area is 205m to take by weighing Conductex SC Ultra carbon black
2/ g) (average grain diameter is 82nm, and the DBP value is 75cc/100g, and the BET surface area is 31m with Raven 430 carbon blacks
2/ g.) two kinds of carbon black 60 weight portions (both weight ratios are 5: 1), vacuumize, after mixing by ball mill, the toluene solution that adds the compound monoalkoxytitanates coupling agent (CT-136) of 4 weight % mixed on high-speed mixer 2 hours, then with solvent evaporation (consumption of coupling agent be carbon black weight 3%).With the gained mixture join by the polyvinyl butyral resin of 100 weight portions (
B-76) and in the solution formed of the ethyl acetate of 600 weight portions and mix, then to the weight percent concentration that wherein adds 25 weight portions be 40% melamine resin (
717) solution is promptly prepared carbon oil product of the present invention after mixing.
Adopt above-mentioned carbon oil, print out as shown in Figure 2 carbon resistance component by manual silk screen printing on the rigidity wiring board, after 150 ℃ baking 30min solidify down, its resistance is tested, test result is listed in the table 2.
Embodiment 4
(average grain diameter is 30nm, and the DBP value is 174cc/100g, and the BET surface area is 254m to take by weighing the V-XC72 carbon black
2/ g) (average grain diameter is 45nm, and the DBP value is 121cc/100g, and the BET surface area is 42m with the BP280 carbon black
2/ g) two kinds of carbon black 80 weight portions (both weight ratios are 5: 1), vacuumize, after mixing by ball mill, the toluene solution that adds the compound monoalkoxytitanates coupling agent (CT-136) of 4 weight % mixed on high-speed mixer 2 hours, then with solvent evaporation (consumption of coupling agent be carbon black weight 3%).Join the gained mixture in the solution of forming by the methyl ethyl ketone of the polyvinyl butyral resin (ButvarB-76) of 100 weight portions and 800 weight portions and mix, be 10% phenol resin solution then to the weight percent concentration that wherein adds 100 weight portions, promptly prepare carbon oil product of the present invention after mixing.
Adopt above-mentioned carbon oil, print out as shown in Figure 2 carbon resistance component by manual silk screen printing on the rigidity wiring board, after 150 ℃ baking 30min solidify down, its resistance is tested, test result is listed in the table 2.
Fig. 4 is the electron micrograph of the carbon resistance component surface texture of present embodiment preparation, and as can be seen from Figure 4: the carbon resistance component surface of preparing is comparatively regular, does not have blemish such as tangible crackle, pin hole.
Embodiment 5
Adopt V-XC72 and two kinds of carbon black 50 weight portions of BP460, the weight ratio of two kinds of carbon blacks is 41: 9, and other technologies are identical with embodiment 1, make according to carbon oil of the present invention and carbon resistance component.Its resistance is tested, and test result is listed in the table 2.
Embodiment 6
Adopt V-XC72 and two kinds of carbon black 50 weight portions of BP460, the weight ratio of two kinds of carbon blacks is 21: 4, and the dibutyl phthalate that adds 10 weight portions is as plasticizer, and other technologies are identical with embodiment 1, make according to carbon oil of the present invention and carbon resistance component.Its resistance is tested, and test result is listed in the table 2.
Fig. 5 is the electron micrograph of the carbon resistance component surface texture of present embodiment preparation, and as can be seen from Figure 5: the carbon resistance component surface of preparing is comparatively regular, does not have blemish such as tangible crackle, pin hole.
Embodiment 7
Adopt V-XC72 and two kinds of carbon black 50 weight portions of BP460, the weight ratio of two kinds of carbon blacks is 43: 7, and other technologies are identical with embodiment 1, make according to carbon oil of the present invention and carbon resistance component.Its resistance is tested, and test result is listed in the table 2.
Embodiment 8
Adopt V-XC72 and two kinds of carbon black 50 weight portions of BP460, the weight ratio of two kinds of carbon blacks is 22: 3, and other technologies are identical with embodiment 1, make according to carbon oil of the present invention and carbon resistance component.Its resistance is tested, and test result is listed in the table 2.
Embodiment 9
Adopt V-XC72 and two kinds of carbon black 150 weight portions of BP460, the weight ratio of two kinds of carbon blacks is 4: 1, add 100 weight portion weight percent concentration and be 10% phenolic resins (
EP560) solution, other technologies are identical with embodiment 6, make according to carbon oil of the present invention and carbon resistance component.Its resistance is tested, and test result is listed in the table 2.
Embodiment 10
Adopt V-XC72 and two kinds of carbon black 200 weight portions of BP460, the weight ratio of two kinds of carbon blacks is 4: 1, add 100 weight portion weight percent concentration and be 25% phenolic resins (
EP560) solution, other technologies are identical with embodiment 6, make according to carbon oil of the present invention and carbon resistance component.Its resistance is tested, and test result is listed in the table 2.
Comparative example 1
Adopt the method identical with embodiment 1, different is that employed carbon black is single V-XC72 (particle diameter is 30nm, and DBP value is 174cc/100g, and the BET surface area is 254m2/g) carbon black 30 weight portions, prepares carbon oil and carbon resistance component accordingly.Its resistance is tested, and test result is listed in the table 2.Data from table 2 deviation of resistance as can be seen are bigger, and the resistance consistency of carbon resistance component is relatively poor.
Comparative example 2
With 100 ohm-sq/25 μ m ± 10%; After the carbon oil of 1000 ohm-sq/25 μ m ± 10% two kind of specifications mixes according to 1: 4 ratio, obtain the carbon oil of this Comparative Examples.Adopt the method identical with embodiment 1 to make corresponding carbon resistance component then, its resistance is tested, test result is listed in the table 2.
Fig. 6 is the electron micrograph of the surface texture of the carbon resistance component prepared, and as can be seen from Figure 6: there is the blemish of tangible pin hole form in the carbon resistance component surface of preparing, thereby has influenced the thermal stability of carbon resistance component and the stability of internal resistance.
Following table 1 is the sized data of prepared carbon resistance component, and table 2 is the resistance measurement result.
Table 1, carbon resistance size results
| Length (mm) | Width (mm) | Thickness (μ m) | |
| Embodiment 1,2,3 | 1.33～1.36 | 0.52～0.55 | 9～11 |
| Embodiment 4 | 1.33～1.36 | 0.52～0.55 | 10～11 |
| Embodiment 5 | 1.33～1.36 | 0.52～0.55 | 8～10 |
| Embodiment 6,9,10 | 1.33～1.36 | 0.52～0.55 | 9～10 |
| Embodiment 7 | 1.33～1.36 | 0.52～0.55 | 8～10 |
| Embodiment 8 | 1.33～1.36 | 0.52～0.55 | 8～10 |
| Comparative Examples 1 | 1.33～1.36 | 0.52～0.55 | 8～10 |
| Comparative Examples 2 | 1.33～1.36 | 0.52～0.55 | 8～10 |
Table 2, (unit is carbon resistance component resistance distribution results: Ω)
| Resistance mean value | Deviation | |
| Embodiment 1 | 11.98K | ±8％ |
| Embodiment 2 | 4.25K | ±6％ |
| Embodiment 3 | 3.19K | ±8％ |
| Embodiment 4 | 2.69K | ±5％ |
| Embodiment 5 | 6.53K | ±5％ |
| Embodiment 6 | 4.90K | ±5％ |
| Embodiment 7 | 4.05K | ±5％ |
| Embodiment 8 | 3.52K | ±6％ |
| Embodiment 9 | 475 | ±5％ |
| Embodiment 10 | 456 | ±5％ |
| Comparative Examples 1 | 9.40K | ±15％ |
| Comparative Examples 2 | 538 | ±15％ |
Claims (30)
1. carbon oil that is used to manufacture carbon resistance component, comprise carbon black, resin binder, crosslinking agent and solvent, it is characterized in that described carbon black adopts bi-component carbon black system, in described bi-component carbon black, wherein a kind of carbon black that conductance and the desired side's resistance of described carbon oil is approaching is as the key component carbon black, regulate the another kind of carbon black of carbon oil side's resistance as the accessory constituent carbon black with being used to accordingly, wherein the consumption of key component carbon black accounts for 70～95 weight % of total carbon black consumption, and the consumption of corresponding accessory constituent carbon black accounts for 5～30 weight % of total carbon black consumption; The selection of described bi-component carbon black one of meets the following conditions:
1) .|d
1-d
2|＞4nm; Or
2).|A
1-A
2|＞50cc/100g；
Wherein: d
1, d
2Be respectively the average grain diameter of two kinds of carbon blacks, the average grain diameter d of described carbon black
1, d
2Be 10～100nm, A
1, A
2Be respectively the DBP value of two kinds of carbon blacks of correspondence, the DBP value A of described carbon black
1, A
2Be 50～250cc/100g;
The content of described carbon black, resin binder, crosslinking agent and solvent is:
Carbon black: 20～200 weight portions,
Resin binder: 100 weight portions,
Crosslinking agent: 5～25 weight portions and
Solvent: 200～1000 weight portions.
2. the carbon oil that is used to manufacture carbon resistance component according to claim 1 is characterized in that the selection of described bi-component carbon black meets the following conditions simultaneously:
1).|d
1-d
2|＞4nm；
2).|A
1-A
2|＞50cc/100g；
Its precondition is: its DBP value of the carbon black component that wherein average grain diameter is little is also big.
3. the carbon oil that is used to manufacture carbon resistance component according to claim 1 is characterized in that described carbon black is acetylene carbon black, oven process carbon black, thermal cracking carbon black and/or channel carbon black.
4. the carbon oil that is used to manufacture carbon resistance component according to claim 1 is characterized in that the consumption of key component carbon black accounts for 80～90 weight % of total carbon black consumption, and the consumption of corresponding accessory constituent carbon black accounts for 10～20 weight % of total carbon black consumption.
5. the carbon oil that is used to manufacture carbon resistance component according to claim 1, it is characterized in that described resin binder is the thermoplastic resin with caoutchouc elasticity, comprise polyvinyl butyral resin, polyvingl ether, poly-IVE, PAUR and/or polyether-type ammonia ester.
6. the carbon oil that is used to manufacture carbon resistance component according to claim 5 is characterized in that described resin binder is a polyvinyl butyral resin.
7. the carbon oil that is used to manufacture carbon resistance component according to claim 1 is characterized in that described crosslinking agent is epoxy resin, epoxy-phenolic resin, phenolic resins, Lauxite, melamine resin, unsaturated polyester resin and/or alkyd resins.
8. the carbon oil that is used to manufacture carbon resistance component according to claim 7 is characterized in that described crosslinking agent is epoxy resin, phenolic resins and/or melamine resin.
9. the carbon oil that is used to manufacture carbon resistance component according to claim 1 is characterized in that described solvent is alcohols, ketone and/or ester class organic solvent.
10. the carbon oil that is used to manufacture carbon resistance component according to claim 9 is characterized in that described alcohols is methyl alcohol, ethanol, normal propyl alcohol or isopropyl alcohol; Described ketone is acetone, methyl ethyl ketone or methyl iso-butyl ketone (MIBK); Described ester class is methyl acetate, ethyl acetate or ro-butyl acetate.
11. the carbon oil that is used to manufacture carbon resistance component according to claim 1 is characterized in that also containing titanate coupling agent or silane coupler, with respect to the resin binder of 100 weight portions, the consumption of this coupling agent is 1～40 weight portion.
12. the carbon oil that is used to manufacture carbon resistance component according to claim 11 is characterized in that described titanate coupling agent is monoalkoxy type titanate coupling agent, monoalkoxy pyrophosphate type titanate coupling agent or huge legendary turtle mould assembly titanate coupling agent; Described silane coupler is amino vinylsilane coupling agent, methacryloxy silane coupler or epoxy silane coupling.
13. the carbon oil that is used to manufacture carbon resistance component according to claim 1 is characterized in that also containing the additive that comprises plasticizer and/or paraffin class processing aid, with respect to the resin binder of 100 weight portions, the consumption of this additive is 5～20 weight portions.
14. the carbon oil that is used to manufacture carbon resistance component according to claim 13 is characterized in that described plasticizer is glycols, fatty acid, phosphoric acid ester or phthalate.
15. the carbon oil that is used to manufacture carbon resistance component according to claim 13 is characterized in that described plasticizer is a dibutyl phthalate.
16. the carbon oil that is used to manufacture carbon resistance component according to claim 1, the range of viscosities that it is characterized in that described carbon oil is 5000～20000mPas.
17. the preparation method of a carbon oil may further comprise the steps:
(1) the square resistance required according to described carbon oil, selecting the close wherein a kind of carbon black of conductance is the key component carbon black, corresponding another kind of carbon black is as the accessory constituent carbon black, then two kinds of carbon blacks are mixed, wherein the consumption of key component carbon black accounts for 70～95 weight % of total carbon black consumption, the consumption of corresponding accessory constituent carbon black accounts for 5～30 weight % of total carbon black consumption, and the selection of described two kinds of carbon blacks one of meets the following conditions:
1) .|d
1-d
2|＞4nm; Or
2).|A
1-A
2|＞50cc/100g；
Wherein: d
1, d
2Be respectively the average grain diameter of two kinds of carbon blacks, the average grain diameter d of described carbon black
1, d
2Be 10～100nm, A
1, A
2Be respectively the DBP value of two kinds of carbon blacks of correspondence, the DBP value A of described carbon black
1, A
2Be 50～250cc/100g;
(2) described carbon black is mixed with the thermoplastic resin solution who is formed by resin binder and solvent;
(3) in step (2) gained mixture, add crosslinking agent and mixing to form pastel;
Wherein, the consumption of described carbon black, resin binder, crosslinking agent and solvent is:
Carbon black: 20～200 weight portions;
Resin binder: 100 weight portions;
Crosslinking agent: 5～25 weight portions;
Solvent: 200～1000 weight portions.
18. method according to claim 17 is characterized in that the selection of described two kinds of carbon blacks meets the following conditions simultaneously:
1).|d
1-d
2|＞4nm；
2).|A
1-A
2|＞50cc/100g；
Its precondition is: its DBP value of the carbon black component that wherein average grain diameter is little is also big.
19. method according to claim 17 is characterized in that described carbon black is acetylene carbon black, oven process carbon black, thermal cracking carbon black and/or channel carbon black.
20. method according to claim 17 is characterized in that the consumption of described key component carbon black accounts for 80～90 weight % of total carbon black consumption, the consumption of corresponding accessory constituent carbon black accounts for 10～20 weight % of total carbon black consumption.
21. method according to claim 17 is characterized in that described resin binder is the thermoplastic resin with caoutchouc elasticity, comprises polyvinyl butyral resin, polyvingl ether, poly-IVE, PAUR and/or polyether-type ammonia ester.
22. method according to claim 17 is characterized in that described crosslinking agent is epoxy resin, epoxy-phenolic resin, phenolic resins, Lauxite, melamine resin, unsaturated polyester resin and/or alkyd resins.
23. method according to claim 17 is characterized in that described solvent is alcohols, ketone and/or ester class organic solvent.
24. method according to claim 23 is characterized in that described alcohols is methyl alcohol, ethanol, normal propyl alcohol or isopropyl alcohol; Described ketone is acetone, methyl ethyl ketone or methyl iso-butyl ketone (MIBK); Described ester class is methyl acetate, ethyl acetate or ro-butyl acetate.
25. method according to claim 17 is characterized in that using titanate coupling agent or silane coupler that carbon black is carried out surface treatment before in step (2).
26. method according to claim 25, it is characterized in that describedly carbon black is carried out surface treatment comprising: at first with carbon black 100～200 ℃ of following vacuum bakeouts 6～24 hours, then carbon black is mixed on high-speed mixer with the toluene solution of described coupling agent, then with solvent evaporation.
27. method according to claim 25 is characterized in that described titanate coupling agent is monoalkoxy type titanate coupling agent, monoalkoxy pyrophosphate type titanate coupling agent or huge legendary turtle mould assembly titanate coupling agent; Described silane coupler is amino vinylsilane coupling agent, methacryloxy silane coupler or epoxy silane coupling.
28. method according to claim 25, the consumption that it is characterized in that described coupling agent is 2～5% of a carbon black total weight.
29. method according to claim 25 is characterized in that adopting dry method that carbon black is carried out surface treatment, promptly directly silane coupler is added in the carbon black of high-speed motion to carry out high-speed mixing.
30. carbon resistance component by any described carbon oil made in the claim 1～16.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100960587A CN100416710C (en) | 2004-11-26 | 2004-11-26 | Carbon oil for producing carbon impedance, its production and carbon impedance component |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100960587A CN100416710C (en) | 2004-11-26 | 2004-11-26 | Carbon oil for producing carbon impedance, its production and carbon impedance component |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1779869A CN1779869A (en) | 2006-05-31 |
| CN100416710C true CN100416710C (en) | 2008-09-03 |
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| CN102856026A (en) * | 2012-09-10 | 2013-01-02 | 临安爱华电子有限公司 | Method for adjusting printed resistor resistance value |
| CN108124388A (en) * | 2017-11-17 | 2018-06-05 | 江门崇达电路技术有限公司 | A kind of wiring board carbon oil printing technology |
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| JP2002038001A (en) * | 2000-07-19 | 2002-02-06 | Nippon Zeon Co Ltd | Rubber composition, crosslinked rubber article, and rubber roll |
| US6479575B1 (en) * | 1999-04-19 | 2002-11-12 | Polytronics Technology Corporation | Electrical devices comprising conductive polymer blend compositions |
| US20040106509A1 (en) * | 2001-03-08 | 2004-06-03 | Tsunemi Ochiai | Refractory raw materials, method for production thereof and refractory using the material |
| US6800126B2 (en) * | 2002-02-12 | 2004-10-05 | The Goodyear Tire & Rubber Company | Preparation and use of composite of rubber and carbon black aggregates and articles of manufacture, including tires, having a component comprised thereof |
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Patent Citations (8)
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|---|---|---|---|---|
| JPH05181322A (en) * | 1991-12-27 | 1993-07-23 | Ricoh Co Ltd | Carrier for electrostatic latent image developer |
| JPH10334454A (en) * | 1997-03-31 | 1998-12-18 | Tdk Corp | Magnetic recording medium |
| JPH11328655A (en) * | 1998-05-13 | 1999-11-30 | Sony Corp | Magnetic recording medium |
| CN1255512A (en) * | 1998-11-27 | 2000-06-07 | 德古萨－希尔斯股份公司 | Products having anti-static function |
| US6479575B1 (en) * | 1999-04-19 | 2002-11-12 | Polytronics Technology Corporation | Electrical devices comprising conductive polymer blend compositions |
| JP2002038001A (en) * | 2000-07-19 | 2002-02-06 | Nippon Zeon Co Ltd | Rubber composition, crosslinked rubber article, and rubber roll |
| US20040106509A1 (en) * | 2001-03-08 | 2004-06-03 | Tsunemi Ochiai | Refractory raw materials, method for production thereof and refractory using the material |
| US6800126B2 (en) * | 2002-02-12 | 2004-10-05 | The Goodyear Tire & Rubber Company | Preparation and use of composite of rubber and carbon black aggregates and articles of manufacture, including tires, having a component comprised thereof |
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