CN100999607B - Electroconductive rubber composition - Google Patents
Electroconductive rubber composition Download PDFInfo
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- CN100999607B CN100999607B CN2007100021188A CN200710002118A CN100999607B CN 100999607 B CN100999607 B CN 100999607B CN 2007100021188 A CN2007100021188 A CN 2007100021188A CN 200710002118 A CN200710002118 A CN 200710002118A CN 100999607 B CN100999607 B CN 100999607B
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- carbon black
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/006—Additives being defined by their surface area
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
Abstract
The aim of the invention is to provide a silastic composition which has excellent processability and excellent conductivity. The conductive silastic composition is characterized in that the composition is obtained by mixing organopolysiloxzane base polymer, solidifying agent and black pigment, as black carbon, the BET specific surface area is 50-200m<2>/g, DBP oil absorption volume is 120-280ml/100g, and the graphite interlaminar distance representing the graphitizing degree is 0.346-0.349.
Description
Technical field
The present invention relates to have the excellent processibility and the electroconductive rubber composition of high conductivity.
Background technology
So far, the rubber composition that is cured and becomes silicon rubber has been known by people, utilize excellent character such as its weathering resistance, thermotolerance, winter hardiness, electrical insulating property, packaged material, coating material, the pattern that is widely used in electrical/electronic part such as uses at formed material etc.In addition, use also and carried out originally giving electroconductibility for the rubber composition of insulating material.
As above-mentioned method of giving rubber composition electroconductibility, usually methods that adopt the compounding conductive carbon black more.For example, open to have put down in writing in the clear 54-139659 communique (patent documentation 1) the spy and will have 40～100m
2The electroconductibility organopolysiloxane elastomerics of the furnace treated black of the specific surface area of/g (furnace black) and Shawinigan black (acetylene black) and usefulness.In addition, the spy opens and has put down in writing compounding in the clear 55-120656 communique (patent documentation 2) specific surface area is arranged is 900m
2The liquid organopolysiloxane composition of/g sooty above, that have hollow shelly particle.The spy opens and has put down in writing in the clear 55-108455 communique (patent documentation 3) the liquid organopolysiloxane composition of the extrusion moulding type of carbon black and conducting fibre and usefulness.The spy opens to have put down in writing in the clear 56-120761 communique (patent documentation 4) and has used specific surface area to be 80m
2The sooty rubber composition that/g is above.Specially permit to have put down in writing in No. 2731691 communique (patent documentation 5) and used following sooty silicon rubber: adopt oil oven (oil furnace) manufactured, specific surface area is 25～50m
2/ g, the DBP oil number is 100～150ml/100g, the painted permeability of toluene is 90～100%.If classify according to its manufacture method at the above-mentioned carbon black that uses under the purpose of electroconductibility of giving, be divided into pyrolytic carbon black (thermal black), furnace treated black, Shawinigan black etc.
In addition, as the method for giving high conductivity, knownly as putting down in writing in the special fair 3-47663 communique (patent documentation 6), use the silicoorganic compound that contain phenyl, perhaps ring-type or the directly catenate organopolysiloxane and method such as dilute of a large amount of use polymerization degree 10 below as record in the special fair 4-28009 communique (patent documentation 7).But the former impairs the original winter hardiness of silicon rubber, physical property owing to use the silicoorganic compound that contain phenyl, and has the problem because of the difference rerum natura fluctuation of compounding process.In addition, the latter's being punctured into more than several % when molded can not be said so and can be stood practical technology.
In addition, the common carbon black distinguished mutually of compounding and conductive carbon black in silicon rubber, but their structure degree to the utmost is flourishing, when compounding during in silicon rubber, be difficult to rubber unvulcanizate (rubbercompound) and change, have shortcoming aspect the tackiness when rolling press stalling characteristic, flakiness, roller tackiness, rubber unvulcanizate keeping on polyethylene sheets more.
In view of above situation, strong hope is established excellent in workability, is had the technology of the rubber composition of satisfactory electrical conductivity.
Patent documentation 1: the spy opens clear 54-139659 communique
Patent documentation 2: the spy opens clear 55-120656 communique
Patent documentation 3: the spy opens clear 55-108455 communique
Patent documentation 4: the spy opens clear 56-120761 communique
Patent documentation 5: specially permit communique No. 2731691
Patent documentation 6: special fair 3-47663 communique
Patent documentation 7: special fair 4-28009 communique
Summary of the invention
The present invention In view of the foregoing finishes, and its purpose is the rubber composition that excellent in workability is provided and has satisfactory electrical conductivity.
Present inventors etc. have carried out conscientiously research to achieve these goals, found that: have in the electroconductive rubber composition of conductive carbon black in compounding, the carbon black that use has specific rerum natura is effective as this carbon black, in this case, the preferred carbon black that adopts specific manufacture method manufacturing described later that uses is effectively, thereby has finished the present invention.
That is, the invention provides electroconductive rubber composition, it is characterized in that: organopolysiloxane base polymer, solidifying agent and carbon black compounding are formed, and as carbon black, the BET specific surface area is 50～200m
2/ g, the DBP oil number is 120～280ml/100g, and the graphite layers of expression degree of graphitization (graphitization degree) is 0.346～0.349nm apart from d (002).
The excellent electric conductivity of electroconductive rubber composition of the present invention, even and improve mixing intensity and carry out mixingly by force, in rubber unvulcanizate, not having adhesion sense yet, carry out two roller processing easily, even and be clamped in the polyethylene sheets uncrosslinked rubber keeping, the sheet material adhesion is few, and processibility is good.
Embodiment
Electroconductive rubber composition of the present invention is that compounding is satisfied the conductive carbon black of following condition and cooperated various additives etc. as required in rubber composition basically, and described rubber composition contains by adopting normal temperature or heating etc. to make its curing become the organopolysiloxane base polymer and the solidifying agent of rubber elastomer.
The meaning that quality characteristic comprised of above-mentioned conductive carbon black is as follows.That is, the sooty that uses among the present invention first is characterized as: the BET specific surface area is 50～200m
2/ g, the DBP oil number is 120～280ml/100g, and the graphite layers of expression degree of graphitization is 0.346～0.349nm apart from d (002).
As such carbon black, preferably adopt the carbon black of oil firing manufactured, the oil firing reaction of described oil firing method in carbon black manufacturing process stops not comprise in the operation chilling operation that adopts water.
Carbon black is generally classified by method for making, can be divided into oven process, channel process, pyrolysis method (comprising the Shawinigan black method) etc.So-called oven process carries out then the spittle being carried out the method for water-cooled by the partial combustion in the space of suitable turbulent diffusion raw material encirclement to the creosote wet goods in refractory chamber, adopts the carbon black of this method manufacturing to be called furnace treated black.So-called channel process is not have besieged space that diffusion flame is carried out partial combustion, and the method for making that itself and huyashi-chuuka (cold chinese-style noodles) (frid) are collided adopts the carbon black of this method manufacturing to be called thermally oxidized black.So-called pyrolysis method, be in advance the checkers buildings of refractory brick fully to be heated, therein with raw material pyrolysated method or method for making similar with it, adopt the carbon black of this method manufacturing to be called the pyrolysis method carbon black, will in pyrolysis method, adopt the carbon black of the manufacture method manufacturing of the exothermic decomposition of acetylene in besieged space to be called Shawinigan black especially.
The carbon black that uses among the present invention is preferably the carbon black that adopts the oil firing manufactured, and described oil firing method stops not contain in the operation chilling operation that adopts water in the oil firing reaction.It is similar to the oil oven method, but can be described as the visibly different carbon black of method for making.This technology can be buied ENSACO260G, ENSACO250G, ENSACO210G (selling) as known with the carbon black of being produced by the title of the MMM Process method of present ス イ ス TIMCAL society management.As the sooty feature that adopts MMM Process manufactured, it comprises: the BET specific surface area can be at 50～1000m
2The wide region inner control of/g, and owing to do not have the chilling operation that adopts water, so the sooty structure is higher, DBP oil number height (120～280ml/100g), because combustion reactions stops not contain the chilling operation that adopts water in the operation, so sooty degree of graphitization height.
For the compounding of carbon black in organosilicon polymer, Shawinigan black is the degree of graphitization height on method for making, particularly forms graphite crystallization portion at carbon blacksurface, and therefore poor with the affinity of silicone based polymkeric substance, compounding is poor.Therefore, the compounding of Shawinigan black in organosilicon polymer is when mixing deficiency, and rubber unvulcanizate is difficult to tangle, if mixing consumingly, strong shearing force makes rubber unvulcanizate produce tackiness.
Big event when the tackiness of uncrosslinked rubber unvulcanizate is Rubber processing adheres to the dispersed variation that makes linking agent on two rollers, when keeping in blocks is in polyethylene sheets, produces the film difficulty and peels off the problem of processing that waits.
On the other hand, furnace treated black structure on method for making is low, need the heavy addition carbon black when therefore making its conduction with furnace treated black, separately carbon black is carried out mixing until the loading level that manifests conductivity level, the compounding rubber difficulty, and, therefore need big shearing force equally with Shawinigan black owing to adding a large amount of carbon blacks, in rubber unvulcanizate, produce big tackiness equally.
Carbon black compounding by will adopting MMM Process manufactured such as present inventor is in rubber composition, latest find can be with the carbon black addition realization high conductivity same or few with Shawinigan black, and the tackiness of the uncrosslinked rubber unvulcanizate of compounding is little, excellent in workability.
The carbon black that uses among the present invention, be important document with following: the BET specific surface area is 50～200m
2/ g.Wherein, so-called specific surface area is with the surface-area (m of per unit mass carbon black (g)
2) expression.
Sooty BET specific surface area of the present invention is 50～200m
2/ g is preferably 50～100m
2/ g.The sooty electroconductibility height that the BET specific surface area is big, a small amount of just easy embodiment electroconductibility, but the compounding in polymkeric substance is poor, and it is difficult that compounding rubber becomes.
In addition, in the present invention, the value of this sooty DBP oil number is defined as 120～280ml/100g.So-called DBP oil number by the degree in conjunction with the complicated agglutinative structure that produces chemistry, physics, is meant the ml number of the oil that every 100g carbon black is comprised between each particle of expression carbon black.Wherein, DBP is a dibutyl phthalate.
The DBP oil number 60～150ml/100g of the value 120～280ml/100g of DBP oil number of the present invention and oven process blackout compares, and is more near the value of the DBP oil number 70～300ml/100g of Shawinigan black.
Above-mentioned DBP oil number is preferably 120～250ml/100g, more preferably 150～200ml/100g.When the DBP oil number was high, if give strong shearing force when compounding of polymers, thereby the then destructurized electroconductibility that makes reduced, and the reproducibility of the electroconductibility of rubber cured article is poor.The carbon black that the DBP oil number is little is difficult for manifesting electroconductibility, needs heavy addition.The sooty properties specify of above-mentioned record is in JIS K 6217 " rubber grade carbon black-fundamental characteristics-".
In addition, known carbon black carries out greying (graphitization) by method for making difference, 2 thermic devices.The graphite layers of so-called this degree of graphitization of expression is apart from d (002), is used as the crystallinity index of graphite and adopts average graphite layers that X-ray diffraction method obtains apart from d (002) expression degree of graphitization.Adopt sooty d (002) value of MMM Process manufactured to be roughly 0.346～0.349nm, littler than 0.350～0.355nm of furnace treated black, bigger than 0.340～0.344nm of Shawinigan black, just in time be positioned in the middle of it.
Carry out the result of various researchs like this, adopt the carbon black of MMM Process method to possess the feature of the high-specific surface area of the high structure of Shawinigan black and furnace treated black, compounding can obtain good electrical conductivity when organosilicon polymer (organopolysiloxane base polymer).In addition, because degree of graphitization is positioned at the centre of Shawinigan black and furnace treated black, so compounding excellence in organosilicon polymer, compare also with Shawinigan black and to disperse with low-shearing power easily, therefore the tackiness of the silicon rubber gross rubber after the carbon black compounding is little, becomes the electroconductive rubber composition of excellent in workability.
In addition, in the present invention, the compounding amount of above-mentioned carbon black in rubber composition selected arbitrarily according to the polymerization degree of polysiloxane basis polymkeric substance and the characteristic of gained rubber composition, be not particularly limited, usually use 1～200 mass parts with respect to organopolysiloxane base polymer 100 mass parts, preferably in the scope of 5～100 mass parts, use.
Moreover, with raising reinforcement, electroconductibility is purpose, also the carbon black with identical or other kinds is arbitrarily in the carbon black with specific rerum natura that adopts specific manufacture method of the present invention to produce, and the kind of the conductive carbon black of usefulness be not particularly limited, but in the present invention, preferred especially and Shawinigan black is also used, in this case, the above-mentioned specific carbon black of the present invention and the compounding ratio of Shawinigan black are preferably specific carbon black/Shawinigan black=100/0～10/90, are preferably 100/0～30/70 (mass ratio) especially.If Shawinigan black is too much, sheet material adhesion sometimes, compounding deterioration.Moreover, and when using Shawinigan black, the above-mentioned specific carbon black and the ratio of Shawinigan black are preferably 90/10～10/90 as mass ratio.
The above-mentioned sooty rubber composition of compounding of the present invention is with (a) organopolysiloxane base polymer, (b) solidifying agent and compoundings such as various additives as required, makes it to disperse equably to form.In the various compositions that in this rubber composition, use, (a) the organopolysiloxane base polymer and (b) solidifying agent suitably select according to the reaction mechanism that is used to make rubber-like elastic body.As its reaction mechanism, known (1) adopts the cross-linking method of organic peroxide sulfuration agent, the method that (2) adopt the addition method etc., as everyone knows according to its reaction mechanism determine (a) composition and (b) composition, promptly solidify preferably combination with catalyzer or linking agent.
In more detail, as the organopolysiloxane of above-mentioned (a), be the organopolysiloxane that has at least 2 thiazolinyls in a part, with the organopolysiloxane shown in the following average group accepted way of doing sth (1) as host (base polymer).
R
1 aSiO
(4-a)/2 (1)
In the formula, R
1Be the carbon number 1～10 that is same to each other or different to each other, preferred 1～8 non-replacement or 1 valency alkyl of replacement, a is 1.5～2.8, the positive number of preferred 1.8～2.5, more preferably 1.95～2.05 scopes.Wherein, as above-mentioned R
1The shown non-replacement on the Siliciumatom or the monovalence alkyl of replacement of being attached to, can enumerate methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, amyl group, neo-pentyl, hexyl, cyclohexyl, octyl group, nonyl, alkyl such as decyl, phenyl, tolyl, xylyl, aryl such as naphthyl, benzyl, styroyl, aralkyl such as hydrocinnamyl, vinyl, allyl group, propenyl, pseudoallyl, butenyl, hexenyl, cyclohexenyl, thiazolinyls such as octenyl, part or all of the hydrogen atom of these groups is by fluorine, bromine, halogen atoms such as chlorine, the group that cyano group etc. replace, for example chloromethyl, chloropropyl, bromotrifluoromethane, halogen-substituted alkyls such as trifluoro propyl, cyanoethyl etc.Preferred R
180 moles of % above be methyl.
In this case, R
1In at least 2 be necessary for thiazolinyl (preferred carbon number is 2～8, more preferably 2～6).Moreover the content of thiazolinyl is preferably whole organic groups (being the monovalence alkyl of above-mentioned non-replacement or replacement) R
1In 0.0001～20 mole of %, preferred 0.001～10 mole of % is preferably about 0.01～5 mole of % especially.This thiazolinyl can combine with the Siliciumatom of molecule chain end, also can with molecular chain in the middle of (that is) Siliciumatom combination, non-molecule chain end also can combine with both, but preferably contains the Siliciumatom bonded thiazolinyl with molecular chain two ends at least.
There is no particular restriction for the polymerization degree, can use under the normal temperature polymkeric substance as liquid state and even untreated rubber shape, suitable use that common mean polymerisation degree is 50～30000, preferred 100～20000, more preferably about 100～10000 polymkeric substance, but in the present invention, from the aspect of electroconductibility, above-mentioned polysiloxane basis preferred its polymerization degree of polymkeric substance is more than 1000, be called the polymkeric substance of so-called ミ ラ Block Le type.Shear-stress appropriateness when this is considered to owing to mixing more can be brought into play above-mentioned effect by compounding.
In addition, the structure of this organopolysiloxane has main chain and comprises for example two organo-siloxane unit (R such as dimethyl siloxane units, diphenyl siloxane unit, methylphenyl siloxane unit, methyl trifluoro propyl siloxane unit, vinyl methylsiloxane unit basically
1 2SiO
2/2) repeating unit, molecular chain two is terminal with for example three organic siloxy-(R such as trimethylsiloxy, vinyl-dimethyl base siloxy-, divinyl methyl-silicane oxygen base, trivinyl siloxy-, vinyl phenylbenzene siloxy-, vinyl aminomethyl phenyl siloxy-, phenyl dimethylsilane oxygen base, diphenyl methyl siloxy-
1 3SiO
1/2) end capped straight chain structure, but also can partly be structure, ring texture of branch-like etc.
As (b) solidifying agent, under the situation of the cross-linking method of using above-mentioned (1), use benzoyl peroxide, peroxidation 2,4-dichloro-benzoyl, dicumyl peroxide, the peroxidation cumyl tertiary butyl, 2,5-dimethyl-2, various organic peroxide sulfuration agent such as 5-di-t-butyl hexane peroxide, di-t-butyl peroxide, from hanging down the compression permanentset, preferred especially dicumyl peroxide, the peroxidation cumyl tertiary butyl, 2,5-dimethyl-2,5-di-t-butyl hexane peroxide, di-t-butyl peroxide.Moreover these organic peroxide sulfuration agent can be used a kind or use as the mixture more than 2 kinds.
As the compounding amount of the organo-peroxide of (b) composition solidifying agent, with respect to (a) composition polysiloxane basis polymkeric substance 100 mass parts, the scope of preferred 0.05～15 mass parts.If compounding quantity not sufficient 0.05 mass parts of organo-peroxide, then sulfuration might fully not carried out, and carries out compounding even surpass 15 mass parts, does not only have its above effect especially, and gives detrimentally affect to the rerum natura of the silicon rubber that obtains sometimes.
On the other hand, when using the cross-linking method of the addition reaction of adopting above-mentioned (2),, use the combination of following composition as solidifying agent:
(i) contain in a part at least 2 with the organic hydrogen polysiloxanes of Siliciumatom bonded hydrogen atom,
(ii) addition reaction catalyst.
Wherein, as (i) organic hydrogen polysiloxanes, can use shown in the following average group accepted way of doing sth (2), have at least 2, preferred (common about 3～200) more than 3 in a part, more preferably 3～100 Siliciumatoms are in conjunction with the organic hydrogen polysiloxanes of hydrogen atom (SiH yl).
R
2 bH
cSiO
(4-b-c)/2 (2)
(in the formula, R
2Monovalence alkyl for the replacement or the non-replacement of carbon number 1～10.In addition, b, c be satisfy that b is 0.7～2.1, c be 0.001～1.0 and b+c be 0.8～3.0 positive number).
This Siliciumatom can be incorporated in conjunction with hydrogen atom on the Siliciumatom of molecule chain end, also can be incorporated on the Siliciumatom of molecular chain middle (non-molecule chain end), can also be attached on the two.
Wherein, as R
2, can enumerate with formula (1) in R
1Same group does not preferably have aliphatics unsaturated link(age)s such as thiazolinyl.
As above-mentioned organic hydrogen polysiloxanes, can enumerate three (dimethyl hydrogen siloxy-) methyl-monosilane, three (dimethyl hydrogen siloxy-) phenyl silane, 1,1,3, the 3-tetramethyl disiloxane, 1,3,5, the 7-tetramethyl-ring tetrasiloxane, the methyl hydrogen cyclopolysiloxane, methyl hydrogen siloxane dimethyl siloxane cyclocopolymer, the end capped methylhydrogenpolysi,oxane of two terminal trimethylsiloxy, the end capped dimethylsiloxane methylhydrogensiloxacopolymer copolymer of two terminal trimethylsiloxy, the end capped dimethyl polysiloxane of two terminal dimethyl hydrogen siloxyies, the end capped dimethylsiloxane methylhydrogensiloxacopolymer copolymer of two terminal dimethyl hydrogen siloxyies, the end capped methyl hydrogen siloxane diphenyl siloxane of two terminal trimethylsiloxy multipolymer, the end capped methyl hydrogen siloxane diphenyl siloxane of two terminal trimethylsiloxy dimethylsiloxane copolymer, contain (CH
3)
2HSiO
1/2Unit and SiO
4/2Unitary multipolymer, contain (CH
3)
2HSiO
1/2Unit and SiO
4/2Unit and (C
6H
5) SiO
3/2Unitary multipolymers etc., and in these exemplary compounds, part or all of methyl are by aryl, 3,3 such as other alkyl such as ethyl, propyl group, phenyl, the organic hydrogen polysiloxanes that halogen-substituted alkyls such as 3-trifluoro propyl etc. replace etc.
The molecular structure of this organic hydrogen polysiloxanes can be any of straight chain shape, ring-type, branch-like, tridimensional network, can use that Siliciumatom number (or polymerization degree) in 1 molecule is 2～1000, preferred 3～500, preferred especially about 3～300 organic hydrogen polysiloxanes.
The compounding amount of this organic hydrogen polysiloxanes is 0.1～50 mass parts with respect to (a) composition organopolysiloxane base polymer 100 mass parts, is preferably 0.3～30 mass parts especially.
In addition, this organic hydrogen polysiloxanes is with respect to 1 thiazolinyl in (a) composition, and preferably making in the linking agent with Siliciumatom bonded hydrogen atom is 0.5～4.0 amount, more preferably is 1.0～3.0 amount.When 0.5 of the quantity not sufficient of hydrogen atom, the curing of composition can't fully be carried out, and the hardness of cured composition reduces sometimes, if the amount of hydrogen atom surpasses 4.0, the physical properties and the thermotolerance of cured composition descend sometimes.
(ii) the addition reaction catalyst of composition is to be used for promoting the thiazolinyl of (a) composition and (i) catalyzer of the hydrosilylation addition reaction of the SiH base in the composition, as this addition reaction catalyst, can enumerate the platinum class catalyzer such as complex compound, diacetyl acetate platinum of reactant, Platinic chloride and the olefines of platinum black, platinum chloride, Platinic chloride, Platinic chloride and monohydroxy-alcohol, palladium class catalyzer, platinum metal catalysts such as rhodium class catalyzer.Moreover the compounding amount of this addition reaction catalyst can be catalytic amount, preferably with respect to the base polymer of (a) composition, in platinum amount of element (mass conversion), reaches the amount of 1～1000ppm scope.If curing uses the compounding amount of catalyzer as the not enough 1ppm of platinum amount of element, might can't fully be cured, in addition,, can not expect the raising of curing speed etc. especially even surpass 1000ppm.
Moreover, in electroconductive rubber composition of the present invention, can be at any time additionally compounding weighting agent, pigment, thermotolerance rising agent, fire retardant etc., in the scope of not damaging effect of the present invention, can and use other organopolysiloxane.As such material, usually also can add reinforcement weighting agents such as fumed silica, precipitated silica, diatomite arbitrarily, other inorganic conductive materials such as titanium oxide, aluminum oxide, zinc oxide, ferric oxide, cerium oxide, metallic nickel powder, extenders such as mica, clay, zinc carbonate, manganous carbonate, lime carbonate, cerous hydroxide, granulated glass sphere, polydimethylsiloxane, the polysiloxane that contains thiazolinyl, poly organic silicon sesquioxyalkane, silicone rubber powder, releasing agent etc.
In addition, also can add the polymerization degree be below 100 low-molecular-weight siloxane, contain silanol group silane, contain the silane etc. of alkoxyl group as dispersing auxiliary.
In addition, have flame retardant resistance, resistivity against fire in order to make rubber composition of the present invention, in the scope of not damaging the object of the invention, suitably compounding contains material, platinic compound and titanium dioxide, platinum and manganous carbonate, platinum and the γ-Fe of platinum
2O
3, common rubber composition such as ferrite, mica, glass fibre, glass flake additive.
Rubber composition involved in the present invention is by using two rollers, Banbury, De ウ ミ キ サ one compounding rubber machines such as (kneaders) with the mentioned component uniform mixing, implements heat treated as required and makes.In this case, for example, can be in advance with organopolysiloxane, as the mixing such as the silica-based weighting agent of micro mist shape of reinforcement silicon-dioxide, modulate basic rubber unvulcanizate, similarly use the compounding rubber machine that above-mentioned carbon powder is mixed into wherein, further interpolation, mixed curing agent.
The electroconductive rubber composition that makes like this can adopt mould extrusion forming etc. usually the organosilyl various methods of forming of moulding be shaped to needed purposes.Its condition of molding is not particularly limited, preferred 100～400 ℃, 5 seconds～1 hour scope.When 2 sulfurations of the laggard row of moulding, preferably in 150～250 ℃, 1～30 hour scope, carry out 2 sulfurations.
Embodiment
Embodiment below is shown, and the present invention will be described, but the present invention is not limited by these embodiment.Moreover " part " in the following example is expression " mass parts " all.
[embodiment 1]
Comprising 99.825 moles of % of dimethyl siloxane units and 0.15 mole of % of methyl vinyl siloxane unit, molecular chain two terminal is in 100 parts of 8000 the organopolysiloxanes with 0.025 mole of % end-blocking of dimethyl vinyl silyl, mean polymerisation degree, adding BET specific surface area 65m
2/ g, DBP oil number 190m l/100g, degree of graphitization d (002) be 60 parts of the carbon black A (TIMCAL (strain) system, trade(brand)name " ENSACO 250G ") of 0.347nm as carbon black in kneader, carry out mixing after, reinstall as 2 of linking agent, 5-dimethyl-2,0.5 part of 5-two (t-butyl peroxy) hexane, carry out uniform mixing, make rubber composition.
[embodiment 2]
Add 50 parts of carbon black A (TIMCAL (strain) system, trade(brand)name " ENSACO 250G ") and BET specific surface area 69m except becoming
2/ g, DBP oil number 125ml/100g, degree of graphitization d (002) are that 10 parts of the Shawinigan black C (electrochemical industry (strain) system, the granular product of trade(brand)name デ Application カ Block ラ Star Network) of 0.342nm are as carbon black, add beyond the mixing, make rubber composition similarly to Example 1.
[embodiment 3]
Except 50 parts of 10 parts of carbon black A (TIMCAL (strain) system, trade(brand)name " ENSACO 250G ") and Shawinigan black C (electrochemical industry (strain) system, the granular product of trade(brand)name デ Application カ Block ラ Star Network) being carried out with this ratio and being used as the carbon black, make rubber composition similarly to Example 1.
[embodiment 4]
Except adding BET specific surface area 55m
2/ g, DBP oil number 155ml/100g, degree of graphitization d (002) be 60 parts of the black B (TIMCAL (strain) system, trade(brand)name " ENSACO210G ") of 0.347nm as outside the carbon black, make rubber composition similarly to Example 1.
[comparative example 1]
As carbon black, do not use carbon black A, use carbon black C (60 parts) separately, similarly make the relatively rubber composition of usefulness with the foregoing description 1.
[comparative example 2]
Replace carbon black A, use BET specific surface area 254m
2/ g, DBP oil number 174ml/100g, degree of graphitization d (002) are the furnace treated black D (CABOT society system, trade(brand)name " Vulcan XC72 ") of 0.354nm, similarly make the relatively rubber composition of usefulness with the foregoing description 1.
[comparative example 3]
Replace carbon black A, use BET specific surface area 50m
2/ g, DBP oil number 180ml/100g, degree of graphitization d (002) are the furnace treated black E (Mitsubishi Chemical's (strain) system, trade(brand)name " #3050B of Mitsubishi ") of 0.352nm, similarly make the relatively rubber composition of usefulness with the foregoing description 1.
The silicon rubber gross rubber that use makes adopts extrusion forming to make the test sheet material.Mold temperature is that 165 ℃/10 minutes, forming pressure are 35kgf/cm
2As post cure, sheet material is carried out 200 ℃, 4 hours hot-air vulcanization, according to 6249 pairs of plasticity numbers of JIS-K, sheet material hardness, differently electrically measure.
In addition, as the evaluation of processibility, carry out viscosity test with polyethylene sheets.This test has supposed in rubber unvulcanizate to add the operation of linking agent, with mixing repeatedly 30 minutes of the above-mentioned rubber unvulcanizate of 200g, carries out after mixing in flakes with 2mm two rollers at interval, and thickness is 2mm.Then, the thick rubber unvulcanizate of above-mentioned 2mm is held on the surface with in the soft polyethylene sheet material (0.1mm) after the washing with alcohol, at 60 ℃/10 minutes, forming pressure 10kgf/cm
2Pressure use down the thick framework of 1mm to be crushed down to the thickness of half.The uncrosslinked sheet material that the 1mm of crushing is thick was placed cooling after 30 minutes, peeled polyethylene sheets from rubber, measured the amount of the silicon rubber gross rubber that is adhered to the polyethylene sheets side.The every 100cm of degree of adhesion
3Rubber unvulcanizate amount (the g/100cm that adheres on the polyethylene sheets
3) estimate.Value when not being adhered on the polyethylene sheets fully is 0g/100cm
3
These measurement results are shown in table 1.In addition, sooty specific surface area, DBP oil number, the graphite layers distance of using in embodiment and the comparative example is shown in table 2.
Table 1
Table 2
| The sample name | The name of an article, sooty feature | Specific surface area (m 2/g) | DBP oil number (ml/100g) | Graphite layers is apart from d (002) nm |
| A | Ensaco250G | 65 | 190 | 0.347 |
| B | Ensaco210G | 55 | 155 | 0.347 |
| C | The granular product of デ Application カ Block ラ Star Network | 69 | 125 | 0.342 |
| D | Vulcan?XC72 | 254 | 174 | 0.354 |
| E | The #3050B of Mitsubishi | 50 | 180 | 0.352 |
| (reference) | SGO-5 | 11 | - | 0.336 |
※ uses powdered graphite as a comparison, with the characteristic of エ ス イ one シ one (strain) system SGO-5 and remember in table 2.
As shown in Table 1, the excellent electric conductivity of electroconductive rubber composition of the present invention (embodiment), even improving mixing intensity carries out mixing by force, in rubber unvulcanizate, there is not the adhesion sense yet, two roller processibilities are easy, even and be held in the polyethylene sheets uncrosslinked rubber is taken care of, sheet material adhesion (to the rubber migration of sheet material) is few, and processibility is good.
Claims (6)
1. electroconductive rubber composition, it is characterized in that: be that organopolysiloxane, solidifying agent and the carbon black compounding that has at least 2 thiazolinyls in a part of 50～30000 forms with the mean polymerisation degree shown in the following average group accepted way of doing sth (1), as carbon black, the BET specific surface area is 50～200m
2/ g, the DBP oil number is 120～280ml/100g, and the graphite layers of expression degree of graphitization is 0.346～0.349nm apart from d (002), above-mentioned carbon black adopts the oil firing manufactured, the oil firing reaction of described oil firing method in carbon black manufacturing process stops not contain in the operation chilling operation that adopts water
R
1 aSiO
(4-a)/2 (1)
In the formula, R
1Be the 1 valency alkyl that the non-replacement or the halogen of the carbon number 1～10 that is same to each other or different to each other replaces, a is the positive number of 1.5～2.8 scopes.
2. the described electroconductive rubber composition of claim 1, it is characterized in that: above-mentioned sooty BET specific surface area is 50～100m
2/ g, the DBP oil number is 150～230ml/100g.
3. claim 1 or 2 described electroconductive rubber compositions, wherein, compounding has carbon black in rubber composition, and described rubber composition contains:
(a) mean polymerisation degree shown in the following average group accepted way of doing sth (1) is the organopolysiloxane that has at least 2 thiazolinyls in a part of 1000～30000: 100 weight parts,
R
1 aSiO
(4-a)/2 (1)
In the formula, R
1Be the 1 valency alkyl that the non-replacement or the halogen of the carbon number 1～10 that is same to each other or different to each other replaces, a is the positive number of 1.5～2.8 scopes,
(b) solidifying agent: make (a) organopolysiloxane solidified significant quantity.
4. the described electroconductive rubber composition of claim 3, wherein, (b) solidifying agent of composition is an organo-peroxide, being the scope compounding of 0.05～15 weight part with respect to (a) composition 100 weight parts.
5. electroconductive rubber composition claimed in claim 3; Wherein, (b) curing agent of composition is shown in the following average group accepted way of doing sth (2), has at least 2 silicon atoms in a part in conjunction with the combination of organic hydrogen polysiloxanes and the addition reaction catalyst of hydrogen atom; The compounding amount of above-mentioned organic hydrogen polysiloxanes is 0.1～50 weight portion with respect to (a) composition 100 weight portions; The compounding amount of addition reaction catalyst is with respect to (a) composition; Be scaled the scope of 1～1000ppm with weight as the platinum amount of element
R
2 bH
cSiO
(4-b-c)/2 (2)
In the formula, R
2Be the monovalence alkyl of the non-replacement or the replacement of carbon number 1～10, b, c be satisfy that b is 0.7～2.1, c is 0.001～1.0, b+c is 0.8～3.0 positive number.
6. the described electroconductive rubber composition of claim 3, wherein, sooty compounding amount is 1～200 weight part with respect to organopolysiloxane 100 weight parts.
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| JP2006003495 | 2006-01-11 | ||
| JP2006003495A JP2007186544A (en) | 2006-01-11 | 2006-01-11 | Electroconductive silicone rubber composition |
| JP2006-003495 | 2006-01-11 |
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| CN100999607B true CN100999607B (en) | 2011-10-26 |
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| KR (1) | KR20070075272A (en) |
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| JP6191549B2 (en) * | 2013-08-09 | 2017-09-06 | 信越化学工業株式会社 | Conductive liquid silicone rubber composition and normal temperature shrinkable rubber member for high voltage cable |
| CN106928725A (en) | 2015-12-31 | 2017-07-07 | 蓝星有机硅（上海）有限公司 | conductive curable organic silicon rubber |
| JP7073110B2 (en) | 2017-01-30 | 2022-05-23 | キヤノン株式会社 | Additive-curing liquid silicone rubber mixture, electrophotographic components and their manufacturing methods, and fixing devices |
| EP3613808A4 (en) * | 2017-04-18 | 2021-01-13 | Shin-Etsu Chemical Co., Ltd. | High dielectric insulating silicone rubber composition and electric field relaxation layer |
| JP6888593B2 (en) * | 2018-08-29 | 2021-06-16 | 信越化学工業株式会社 | Mirable type silicone rubber composition and electric field relaxation layer |
| KR20220051844A (en) * | 2019-08-21 | 2022-04-26 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Millable silicone rubber composition, cured silicone rubber, and electrical insulation member for power cable connection |
| CN110437623A (en) * | 2019-09-02 | 2019-11-12 | 贵州航天精工制造有限公司 | A kind of tear-proof high-conductivity silicon rubber and its processing method |
| US20210383942A1 (en) | 2020-06-03 | 2021-12-09 | Eikem Silicones USA Corp. | Method and compositions to achieve long-term stable electrical conductivity in silicone material with carbon black as conductive fillers |
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| US20020037955A1 (en) * | 1998-11-27 | 2002-03-28 | Degussa-Huels Ag | Product with antistatic properties |
| CN1443806A (en) * | 2002-03-12 | 2003-09-24 | 信越化学工业株式会社 | Silicon rebber sheet material with heat-resistance heat-conductivity for thermocopression seal |
| CN1511878A (en) * | 2002-12-27 | 2004-07-14 | 狮王株式会社 | Conductive thermoplastic resin composition |
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| JP2631572B2 (en) * | 1990-04-27 | 1997-07-16 | 東芝シリコーン株式会社 | Conductive silicone rubber composition |
| JP2731691B2 (en) * | 1993-04-26 | 1998-03-25 | 東芝シリコーン株式会社 | Conductive silicone rubber composition |
| US5902517A (en) * | 1996-10-28 | 1999-05-11 | Cabot Corporation | Conductive polyacetal composition |
| JPH10298433A (en) * | 1997-04-28 | 1998-11-10 | Matsushita Electric Works Ltd | Silicone rubber composition and heat-radiating sheet |
| JP2002088256A (en) * | 2000-09-18 | 2002-03-27 | Polymatech Co Ltd | Thermally conductive polymeric composition and thermally conductive molded product |
| US6852790B2 (en) * | 2001-04-06 | 2005-02-08 | Cabot Corporation | Conductive polymer compositions and articles containing same |
| DE10253399A1 (en) * | 2002-11-15 | 2004-05-27 | Eramet & Comilog Chemicals S.A. | Metal-coated carbon black, useful as ferromagnetic material or in e.g. medical valve applications, involve use of nickel, iron, cobalt, yttrium, copper or iridium as the metal |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20020037955A1 (en) * | 1998-11-27 | 2002-03-28 | Degussa-Huels Ag | Product with antistatic properties |
| CN1443806A (en) * | 2002-03-12 | 2003-09-24 | 信越化学工业株式会社 | Silicon rebber sheet material with heat-resistance heat-conductivity for thermocopression seal |
| CN1511878A (en) * | 2002-12-27 | 2004-07-14 | 狮王株式会社 | Conductive thermoplastic resin composition |
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| JP2007186544A (en) | 2007-07-26 |
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