CN1821309B - Insulation silicon rubber compound - Google Patents
Insulation silicon rubber compound Download PDFInfo
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- CN1821309B CN1821309B CN2006100092615A CN200610009261A CN1821309B CN 1821309 B CN1821309 B CN 1821309B CN 2006100092615 A CN2006100092615 A CN 2006100092615A CN 200610009261 A CN200610009261 A CN 200610009261A CN 1821309 B CN1821309 B CN 1821309B
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
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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
- C08K2201/017—Additives being an antistatic agent
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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
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2201/00—Properties
- C08L2201/06—Biodegradable
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
Abstract
The present invention relates to an insulative silicone rubber composition with excellent antistatic properties, comprising 100 parts by mass of a thermosetting silicone rubber composition and 0.0001-5 parts by mass of an ionic conductive antistatic agent such as one or more kinds of lithium salts selected from LiBF4, LiCLO4, LiPF6, LiAsF6, LiSbF6, LiSO3CF3, LiN(SO2CF3)2, LiSO3C4F9, LiC(SO2CF3) 3 and LiB(C6H5) 4. The present invention is aimed to obtain an insulative silicone rubber composition that becomes a silicone rubber maintaining insulation properties, excellent antistatic properties and maintaining antistatic properties even being exposed to a high temperature.
Description
Technical field
The present invention relates to a kind of thermohardening type rubber composition, particularly relate to not only in room temperature but also also have the insulating silicon rubber composition of sufficient antistatic performance at high temperature.
Background technology
Silicon rubber is owing to have characteristics such as good weathering resistance, electrical characteristic, low compression set, thermotolerance, winter hardiness, be widely used in headed by electronic machine, automobile, building, medical treatment, the food etc. various fields.For example, can enumerate the push button pad that uses as the rubber contact of telemanipulator, type-writer, Word message handler, terminal, musical instrument etc.; Pad for building; The vibration-proof rubber of acoustics etc.; The purposes such as mould of packing material, bread and dessert that the mini disc that uses in junctor gasket, sparking plug protective guard trolley part, the computers such as (ス パ one Network プ ラ グ Block one Star) is used.Now, the demand of silicon rubber in continuous increase, is wished to develop the silicon rubber with good characteristic.
These silicon rubber are generally supplied with the form of the composition of enhancing property packing material to contain the high-polymerization degree organopolysiloxane.Said composition is by with mixing devices such as two-way mixing machine (De ゥ ミ キ サ one), two rollers, will enhancing property packing material and various dispersant in stock polymer, adjust.Enhancing such as organopolysiloxane and silicon-dioxide packing material is the electrical insulating property material, as the rubber composition that its cooperation is obtained and the silicon rubber of cured article thereof, existence is charged by contacting with various materials, produces the problems such as dust in static or the absorbed air.
In the past, antistatic rubber used polyethers (patent documentation 1) or carbon black (patent documentation 2,3) as antistatic agent.When using polyethers, exist polyethers at pyrolytic decomposition, thereby do not present the problem of sufficient anti-static effect.Particularly, even thermohardening type silicon rubber only carries out known after fixing, anti-static effect also exists hardly.When using carbon black, exist and be difficult to keep electrical insulating property, or be defined as the problem of black.In addition, the spy opens in the 2003-82232 communique (patent documentation 4), proposed to add the semiconductive roller rubber composition of lithium salts, but, exist and to be applicable to if not the megohmite then coating and the remote input units problems such as (キ one パ Star De) of out of use electric wire in semiconductor regions.
[patent documentation 1] special table 2002-500237 communique
[patent documentation 2] special table 2002-507240 communique
[patent documentation 3] spy opens the 2002-327122 communique
[patent documentation 4] spy opens the 2003-82232 communique
Summary of the invention
The object of the present invention is to provide a kind of insulativity of keeping, and excellent electrostatic prevention property, even also can keep the insulating silicon rubber composition of the formation silicon rubber of excellent static electricity resistance in high temperature exposure.
What present inventors concentrated one's attention on to study to achieve these goals found that, by add a small amount of ionic conductivity antistatic agent in the thermohardening type rubber composition, can solve above-mentioned problem, thereby finish the present invention.That is, the invention provides a kind of insulating silicon rubber composition of antistatic performance excellence, it is characterized in that, in thermohardening type rubber composition 100 mass parts, contain ionic conductivity antistatic agent 0.0001～5 mass parts.
The cured article of insulating silicon rubber composition of the present invention can be kept insulativity, and excellent electrostatic prevention property, even also can keep excellent static electricity resistance in high temperature exposure.In addition, also can be free painted.
Embodiment
Explain the present invention below.
As the thermohardening type rubber composition, so long as the rubber composition that can be cured by heating gets final product and does to limit especially, but preferably in molecule, have in the organopolysiloxane of at least 2 alkenyls, cooperate the basic polymkeric substance of weighting agent conduct such as enhancing property silicon-dioxide as required, and preferably adopt addition reaction-type solidifying agent and/or organo-peroxide solidifying agent as solidifying agent.Shape both can be an also liquid-type of beacon (ミ ラ Block Le) type.
[organopolysiloxane that in (A) molecule, has at least 2 alkenyls]
As (A) composition, can use the compound of a following average group accepted way of doing sth (I) expression:
RaSiO
(4-a)/2(I)
(in the formula, R is that identical or different carbonatoms is 1～10 the monovalence alkyl that does not replace or replace, and a is 1.8～2.3 positive number).
Here, R is that identical or different carbonatoms is 1～10, preferred 1～8 the monovalence alkyl that does not replace or replace, particularly, can enumerate methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, amyl group, neo-pentyl, hexyl, cyclohexyl, octyl group, nonyl, carbonatomss such as decyl are 1～10 alkyl, phenyl, tolyl, xylyl, carbonatomss such as naphthyl are 6～10 aryl, benzyl, styroyl, aralkyl such as hydrocinnamyl, vinyl, allyl group, propenyl, pseudoallyl, butenyl, hexenyl, cyclohexenyl, carbonatomss such as octenyl are 2～10 alkenyl, or the hydrogen atom of these groups part or all by fluorine, bromine, halogen atoms such as chlorine, the group that cyano group etc. replace, for example chloromethyl, chloropropyl, bromotrifluoromethane, three chloropropyls, cyanoethyl etc.Wherein, preferable methyl, vinyl, phenyl, trifluoro propyl, and at least 50 moles of % of preferred R or 50 moles of % are above, particularly 80 moles of % or 80 moles of % are above is methyl.At this moment, at least 2 of R is necessary for alkenyl (preferred carbonatoms is 2～8, and being more preferably carbonatoms is 2～6).The content of alkenyl is preferably 0.0001～20 mole of % among the R, preferred especially 0.001～10 mole of %.This alkenyl both can be combined on the Siliciumatom of molecule chain end, also can be combined on the molecular chain intermediary Siliciumatom, can also be combined on both.
A is 1.8～2.3, preferred 1.9～2.1 positive number, and this organopolysiloxane is essentially the straight chain shape, but also can part branch in the scope of not damaging caoutchouc elasticity.About molecular weight, be not particularly limited, all can to use to the high rubber-like substance of viscosity from the fraction that viscosity is low, but in order solidifying, to form rubber-like elastic body, preferred degree of polymerization is 100～100,000, particularly 150～20,000.
In addition, (A) the composition organopolysiloxane both can use a kind, also can use simultaneously the molecular structure and the polymerization degree different more than 2 kinds or 2 kinds.
This organopolysiloxane can be by known method, for example with organo-halogen-silane carry out (being total to) hydrolytic condensation more than a kind or 2 kinds or 2 kinds, or by using alkalescence or an acidic catalyst ring-opening polymerization cyclic polysiloxanes to obtain.
[enhancing property silicon-dioxide]
The thermohardening type rubber composition in order to give physical strength etc., preferably cooperates (B) enhancing property silicon-dioxide in the organopolysiloxane of (A) composition.
As (B) enhancing property silicon-dioxide, can enumerate vapor phase process (smog matter) silicon-dioxide, precipitation (wet type) silicon-dioxide.These silicon-dioxide, preferably the specific surface area of measuring with the BET method is 50m
2/ g or 50m
2The silicon-dioxide that/g is above, preferred especially 100～400m
2The silicon-dioxide of/g.
Such silicon-dioxide also can use as required with surface treatment agents such as organopolysiloxane, silazane, chlorosilane, organoalkoxysilanes surface-treated silicon-dioxide has been carried out on its surface.In addition, when in the organopolysiloxane of (A) composition, cooperating these fine powdered silicon-dioxide, also can cooperate above-mentioned surface treatment agent.
(B) cooperation of composition is arbitrarily, is 0～100 mass parts with respect to organopolysiloxane 100 mass parts of (A) composition, preferred 1～80 mass parts, preferred especially 5～50 mass parts.When use level is very few, can not get sufficient rubbery intensity sometimes.In addition, when with untreated rubber being the ミ ラ Block Le rubber of raw material, processibility reduces sometimes.In addition, when use level is too much, be difficult to sometimes cooperate, the rubber rerum natura also descends sometimes.
The thermohardening type rubber composition, in the scope of not damaging the application's purpose, except mentioned component, can also add crushed quartz as required arbitrarily, crystallinity silicon-dioxide, diatomite, weighting agents such as lime carbonate, tinting material, the tear strength rising agent, thermotolerance such as ferric oxide or cerium oxide rising agent, titanium oxide, flame retardant resistance rising agents such as platinic compound, be subjected to sour agent, thermal conductivity such as aluminum oxide or boron nitride rising agent, releasing agent, the organoalkoxysilane and the hydrolyzate thereof that particularly contain phenyl as weighting agent with the various organoalkoxysilanes of dispersion agent, diphenyl silanodiol, the charcoal functional silanes, known weighting agent or additive that the low molecular weight polyorganosiloxane of siliceous alcohol radical etc. uses in the thermohardening type rubber composition.
[solidifying agent]
As (C) solidifying agent, as mentioned above, can enumerate (C-1) addition reaction-type solidifying agent, (C-2) organo-peroxide solidifying agent.
As (C-1) addition reaction-type solidifying agent, can make up organic hydride polysiloxane and hydrosilylation catalyst and use.
Hydrosilylation catalyst is the catalyzer that makes the Siliciumatom bonded hydrogen atom (SiH yl) of the alkenyl of (A) composition and organic hydride polysiloxane carry out addition reaction.
As hydrosilylation catalyst, can enumerate platinum metals class catalyzer, i.e. platinum metals simple substance and compound thereof, this catalyzer can use the known material of catalyzer as former addition reaction curing rubber composition.For example, can enumerate the alcoholic solution, palladium catalyst, rhodium catalyst of the microgranular platinum that adsorbs on the carriers such as silicon-dioxide, aluminum oxide or silica gel, platinum chloride, Platinic chloride, Platinic chloride 6 water salt etc., but preferred platinum or platinic compound.The addition of catalyzer as long as can promote addition reaction, is converted into platinum metals amount usually, and the scope of using with respect to the organopolysiloxane of (A) composition is 1ppm～1 weight %, but the scope of preferred 10～500ppm.When addition is lower than 1ppm, can not fully promote addition reaction, insufficient when being solidified with, on the other hand, when greater than 1 weight %, even add more, also few to reactive influence, it is uneconomical often to become.
As the organic hydride polysiloxane, as long as contain more than 2 or 2 in 1 molecule, preferred SiH base more than 3 or 3 gets final product, can be that straight chain shape, ring-type, a catenate are any, linking agent as addition reaction curing rubber composition, known organic hydride polysiloxane can be used, for example, the organic hydride polysiloxane of following column average composition formula (II) expression can be adopted:
R
1 pH
qSiO
(4-P-q)/2(II)
In an above-mentioned average group accepted way of doing sth (II), R
1The monovalence alkyl that expression does not replace or replaces both can be the same or different, preferably the group except the aliphatics unsaturated link(age).Usually, preferred carbonatoms is 1～12, particularly 1～8 alkyl, particularly, can enumerate alkyl such as methyl, ethyl, propyl group, cycloalkyl such as cyclohexyl, alkenyls such as vinyl, allyl group, butenyl, hexenyl, aryl such as phenyl, tolyl, aralkyl such as benzyl, 2-phenylethyl, 2-phenyl propyl, and part or all group that is replaced by halogen atom of the hydrogen atom of these groups, for example 3,3,3-trifluoro propyl etc.In addition, p, q are for satisfying the positive number of 0≤p＜3, preferred 1≤p≤2.2,0＜q≤3, preferred 0.002≤q≤1,0＜p+q≤3, preferred 1.002≤p+q≤3.
The organic hydride polysiloxane has 2 or 2 above SiH bases, preferably has more than 3 or 3 in 1 molecule, this group both can be at molecule chain end, also can also be in both in the middle of molecular chain.In addition, as this organic hydride polysiloxane, be 0.5～10 25 ℃ viscosity, 000cSt, preferred especially 1～300cSt.
As such organic hydride polysiloxane, particularly, can enumerate compound with following structural formula:
[changing 1]
(in the formula, k is 2～10 integer, and s and t are 0～10 integer).
The use level of above-mentioned organic hydride polysiloxane is with respect to (A) composition 100 weight parts, preferred 0.1～40 weight part.In addition, with respect to the aliphatics unsaturated link(age) (alkenyl and dialkylene etc.) of 1 (A) composition, the ratio of bonded hydrogen atom on the Siliciumatom (≡ SiH) is that 0.5～10 scope is suitable, is preferably 0.7～5 scope.When being lower than 0.5, crosslinked insufficient, can not obtain sufficient mechanical sometimes, and when greater than 10 the time, the physical property after the curing reduces, particularly thermotolerance and compression set characteristic variation sometimes.
In addition, except that above-mentioned catalyzer,, also can use addition-crosslinked control agent in order to adjust curing speed.Particularly, can enumerate alkynol class control agents such as ethynylcyclohexanol or Fourth Ring methylvinyl-polysiloxane etc.
As (C-2) organo-peroxide, for example, can enumerate benzoyl peroxide, 2, the 4-dichlorobenzoperoxide, to methyl benzoyl peroxide, adjacent methyl benzoyl peroxide, 2,4-dicumyl peroxide, 2, two (2, the 5-t-butyl peroxy) hexanes of 5-dimethyl, ditertiary butyl peroxide, peroxidized t-butyl perbenzoate, 1,6-hexylene glycol dual-tert-butyl peroxycarbonates etc.
The addition of organo-peroxide is 0.1～10 weight part with respect to (A) composition 100 weight parts, preferred especially 0.2～5 weight part.
The thermohardening type rubber composition, can obtain by mentioned component is mixed with known mixing rolls such as kneader, banbury mixers, two rollers, but usually preferably with the organopolysiloxane of (A) composition with after the enhancing silicon-dioxide of (B) composition mixes, add the solidifying agent of (C) composition.
The thermohardening type rubber composition also can use commercially available material.
Contained ionic conductivity antistatic agent in the application's the insulating silicon rubber composition is not electron conduction materials such as carbon black, so long as the ionic conductivity material can and not be particularly limited, but preferred lithium salts.
Particularly, can enumerate LiBF
4, LiClO
4, LiPF
6, LiAsF
6, LiSbF
6, LiSO
3CF
3, LiN (SO
2CF
3)
2, LiSO
3C
4F
9, LiC (SO
2CF
3)
3, LiB (C
6H
5)
4Deng.These both can use separately, also can use simultaneously more than 2 kinds or 2 kinds.
The ionic conductivity antistatic agent, in order to improve the dispersiveness in the thermohardening type rubber composition, the effect of playing stably is preferably carried out gelatinization with organopolysiloxane.At this moment, organopolysiloxane both can be identical with (A) composition also can be different, both can be that the untreated rubber shape also can be an oily.Preferably dimethyl polysiloxane, methylvinyl-polysiloxane.In addition, in order to improve processing property, in this paste, can also add weighting agents such as enhancing property silicon-dioxide or diatomite.Preferred 2～90 quality % of the concentration of the ionic conductivity antistatic agent in the paste are more preferably 5～80 quality %, preferred especially 10～50 quality %.
The addition of ionic conductivity antistatic agent is 0.0001～5 mass parts with respect to thermohardening type rubber composition 100 mass parts, and preferred 0.0005～3 mass parts is more preferably 0.001～1 mass parts, preferred especially 0.001～0.5 mass parts.When being lower than 0.0001 mass parts, anti-static effect is insufficient, and when greater than 5 mass parts, can not keep insulativity, or the rerum natura of silicon rubber and thermotolerance etc. are brought detrimentally affect.
Ionic antistatic agent both can be added in the thermohardening type rubber composition, also can add when thermally conductive silicone rubber composition is made.
Insulating silicon rubber composition of the present invention becomes the silicon rubber of insulativity excellence by being heating and curing.As forming method, can select known shaping corresponding to shape and size as the moulded products of purpose.For example, can enumerate methods such as injection moulding, compressed moulding, injection molding, calendering formation, extrusion moulding, coating, silk screen printing.As condition of cure, also can be known condition in the various forming methods, generally at 60 ℃～450 ℃ temperature compacted under about several seconds～1 day.In addition, in order to reduce the compression set of cured article, or residual low molecular weight polyorganosiloxane composition in the reduction silicon rubber, or remove resolvent of organo-peroxide etc., can be more than 200 ℃ or 200 ℃, in preferred 200 ℃～250 ℃ baking oven etc., carry out more than 1 hour or 1 hour, preferred about 1 hour～70 hours, be more preferably 1 hour～10 hours after fixing (regelate).
The volume specific resistance of cured article is 1G Ω m or more than the 1G Ω m, and preferred especially 2G Ω m or more than the 2G Ω m in electric wire coating, remote input units purposes etc., can reach the dielectric level that can fully use.
In addition, as antistatic performance, can use the special formula electrostatic tester (シ シ De static (strain) manufacturing) in Nice difficult to understand, on the silicon rubber formed object surface, behind the static by corona discharge charging 6kV, this static voltage reached the time (transformation period) of half in 2 minutes, particularly 1 minute with interior be preferred.
Embodiment
Embodiment and comparative example are shown below, specify the present invention, but the present invention is not limited by the following examples.
Carried charge and volume resistance are measured by following method.
Carried charge is measured
Adopt the special formula static charge tester (シ シ De static (strain) manufacturing) in Nice difficult to understand,, behind corona discharge generation static, measure this static voltage and reach the time of half the forming composition surface.
Volume resistance is measured
Measure according to JIS-K6249.
As following preparation antistatic agent paste.
[preparation of antistatic agent paste]
Is 110m with end with end capped dimethyl polysiloxane untreated rubber 42 mass parts of dimethyl vinylsiloxane base, specific surface area
2The carrying out of/g the fumed silica (R-972, Japanese ア エ ロ ジ Le (strain) is made) handled of hydrophobization, the LiN (SO that contains 20 quality %
2CF
3)
2Adipic acid ester 50 mass parts carry out mixing, preparation antistatic agent paste 1.
With end end capped dimethyl polysiloxane untreated rubber 42 mass parts of dimethyl vinylsiloxane base, specific surface area 110m
2Fumed silica (the R-972 that the hydrophobization of/g was handled, Japan's ア エ ロ ジ Le (strain) is made) 8 mass parts, be the polyether modified silicon oil (KF351F of 75cs 25 ℃ viscosity, SHIN-ETSU HANTOTAI's chemical industry (strain) is made) 50 mass parts carry out mixing, preparation antistatic agent paste 2.
[embodiment 1]
It is 200m that interpolation is made of 99.825 moles of % of dimethyl siloxane units, 0.15 mole of % of methyl vinyl siloxane unit, the 0.025 mole of % in dimethyl vinylsiloxane unit, mean polymerisation degree is about 6000 organopolysiloxane 100 mass parts, BET specific surface area
2The fumed silica of/g (ア エ ロ ジ Le 200, Japan's ア エ ロ ジ Le (strain) is made) 45 mass parts, as two ends of dispersion agent have silanol groups, mean polymerisation degree is 15, is dimethyl polysiloxane 10 mass parts of 30cs 25 ℃ viscosity, mixing with kneader, 170 ℃ of heat treated 2 hours, compositions formulated.
With respect to said composition 100 mass parts, add 0.05 mass parts antistatic agent paste 1, as 2 of linking agent, two (t-butyl peroxy) hexane 0.4 mass parts of 5-dimethyl are behind two roller uniform mixing, at 165 ℃, 70kgf/cm
2Carry out Procuring 10 minutes under the condition, make the thick sheet of 2mm.Then, in 200 ℃ baking oven, implement 4 hours postcure.
This silicon rubber is reduced to room temperature, measure carried charge (transformation period), volume resistance.Similarly, the sample of placing 50 hours, 100 hours, 400 hours is similarly measured carried charge, volume resistance in 200 ℃ baking oven.
The results are shown in table 1.
[embodiment 2]
Except the addition with antistatic agent paste 1 changes to 0.01 mass parts, measure carried charge, volume resistance similarly to Example 1.
The results are shown in table 1.
[embodiment 3]
Contain 10 moles of % of methyl vinyl siloxane unit and 90 moles of % of dimethyl siloxane units in two organo-siloxane unit of molecular chain main chain, viscosity is that molecular chain two ends of 500mPas are 110m with the end capped dimethyl siloxane methyl ethylene of trimethylsiloxane group silicone copolymers 100 mass parts, specific surface area
2The carrying out of/g the fumed silica (R-972 that handles of hydrophobization, Japan's ア エ ロ ジ Le (strain) is made) 5 mass parts, crystallinity silicon-dioxide (Network リ ス タ ラ イ ト VX-S, dragon gloomy (strain) is made) 38 mass parts, viscosity is that the molecular chain two of 9mPas is terminal and (be combined in the hydrogen atom on the Siliciumatom: 1.5 mass parts 0.51 quality %) at the dimethyl siloxane hydrogenated methyl silicone copolymers that the non-end of molecular chain has a SiH base, 0.03 part of 1-ethynylcyclohexanol, the coordination compound of Platinic chloride and divinyl tetramethyl disiloxane is converted into the platinum quality, terminal to molecular chain two with the end capped dimethyl siloxane methyl ethylene of trimethylsiloxane group silicone copolymers interpolation 15ppm, compositions formulated.
With respect to said composition 100 weight parts, add 0.1 weight part antistatic agent paste 1, at 120 ℃, 100kgf/cm
2Condition under carry out Procuring in 10 minutes.Then, in 200 ℃ of baking ovens, implement 4 hours after fixing.
This silicon rubber is reduced to room temperature, measure carried charge (transformation period) and volume resistance.Similarly, the sample of placing 50 hours, 100 hours, 400 hours is similarly measured carried charge, volume resistance in 200 ℃ baking oven.
The results are shown in table 1.
[embodiment 4]
Except the addition with antistatic agent paste 1 changes to 0.05 weight part, measure carried charge, volume resistance similarly to Example 3.The results are shown in table 1.
[comparative example 1]
Except not adding antistatic agent, measure carried charge, volume resistance similarly to Example 1.
The results are shown in table 1.
[comparative example 2]
Except using antistatic agent paste 2 replacement antistatic agent pastes 1, measure carried charge, volume resistance similarly to Example 1.
The results are shown in table 1.
[comparative example 3]
Except not adding antistatic agent, measure carried charge, volume resistance similarly to Example 3.
The results are shown in table 1.
[table 1]
(1.2E+12 represents 1.2 * 10
12)
Claims (8)
1. the insulating silicon rubber composition of an antistatic performance excellence is characterized in that, in thermohardening type rubber composition 100 mass parts, contains ionic conductivity antistatic agent 0.0001～5 mass parts, and described ionic conductivity antistatic agent is for being selected from LiBF
4, LiClO
4, LiPF
6, LiAsF
6, LiSbF
6, LiSO
3CF
3, LiN (SO
2CF
3)
2, LiSO
3C
4F
9, LiC (SO
2CF
3)
3, LiB (C
6H
5)
4In lithium salts more than a kind or 2 kinds, described thermohardening type rubber composition comprises:
A composition: general formula R aSiO
(4-a)/2The organopolysiloxane with alkenyl of expression, 100 mass parts, wherein, R is that identical or different carbonatoms is 1～10 do not replace or monovalence alkyl that halogen replaces, a is 1.8～2.3 positive number;
B composition: enhancing property silicon-dioxide, 0～100 mass parts;
The C composition: solidifying agent, solidify significant quantity, and,
The volume specific resistance of the cured article of insulating silicon rubber composition is more than the 1G Ω m, and behind the static by corona discharge charging 6kV, the time that this static voltage reaches half is to be in 2 minutes the transformation period.
2. according to the insulating silicon rubber composition of record in the claim 1, it is characterized in that it is 50～400m that the B composition is selected from the BET specific surface area
2The fumed silica of/g, precipitated silica.
3. according to the insulating silicon rubber composition of record in the claim 1, it is characterized in that the thermohardening type rubber composition is the addition reaction curing.
4. according to the insulating silicon rubber composition of record in the claim 3, it is characterized in that the C composition is C-1: organic hydride polysiloxane and hydrosilylation catalyst are made up and the addition reaction-type solidifying agent of formation.
5. according to the insulating silicon rubber composition of record in the claim 1, it is characterized in that the thermohardening type rubber composition is an organic peroxide curing type.
6. according to the insulating silicon rubber composition of record in the claim 5, it is characterized in that the C composition is C-2: the organo-peroxide solidifying agent.
7. according to the insulating silicon rubber composition of each record in the claim 1～6, it is characterized in that the ionic conductivity antistatic agent is to carry out gelatinization with organopolysiloxane.
8. insulating silicon rubber, this insulating silicon rubber are to obtain at the after fixing that carries out more than 1 hour more than 200 ℃ by the cured article with the insulating silicon rubber composition of each record in the claim 1～7.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP037493/05 | 2005-02-15 | ||
| JP2005037493A JP4905626B2 (en) | 2005-02-15 | 2005-02-15 | Insulating silicone rubber composition and cured product thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1821309A CN1821309A (en) | 2006-08-23 |
| CN1821309B true CN1821309B (en) | 2011-06-08 |
Family
ID=36922891
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2006100092615A Active CN1821309B (en) | 2005-02-15 | 2006-02-15 | Insulation silicon rubber compound |
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| Country | Link |
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| JP (1) | JP4905626B2 (en) |
| KR (1) | KR101295481B1 (en) |
| CN (1) | CN1821309B (en) |
| TW (1) | TWI389978B (en) |
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| JP4873167B2 (en) * | 2006-09-22 | 2012-02-08 | 信越化学工業株式会社 | Condensation reaction curable silicone rubber composition for forming large stretch rolls for industrial use |
| JP2008266412A (en) * | 2007-04-18 | 2008-11-06 | Shin Etsu Chem Co Ltd | Antistatic silicone rubber molding material |
| JP5309714B2 (en) * | 2007-07-04 | 2013-10-09 | 信越化学工業株式会社 | Silicone pressure-sensitive adhesive composition having antistatic properties and silicone pressure-sensitive adhesive tape |
| JP4706868B2 (en) * | 2007-09-03 | 2011-06-22 | 信越化学工業株式会社 | Antistatic micro-contact printing plate |
| US7781555B2 (en) | 2007-09-03 | 2010-08-24 | Shin-Etsu Chemical Co., Ltd. | Microcontact printing stamp |
| TWI457398B (en) | 2007-12-27 | 2014-10-21 | Momentive Performance Mat Jp | Thermosetting Silicone Oxygenated Compounds |
| TWI588210B (en) | 2007-12-27 | 2017-06-21 | 邁圖高新材料日本合同公司 | Thermosetting silicone rubber composition |
| US8222341B2 (en) * | 2009-03-17 | 2012-07-17 | Mearthane Products Corporation | Semi-conductive silicone polymers |
| CN101805521A (en) * | 2010-03-19 | 2010-08-18 | 东莞市宏达新材料有限公司 | Antistatic silica gel composition and preparation method thereof |
| JP5916457B2 (en) | 2012-03-23 | 2016-05-11 | 住友理工株式会社 | Insulating silicone rubber composition |
| JP5835100B2 (en) * | 2012-05-22 | 2015-12-24 | 信越化学工業株式会社 | Antistatic silicone rubber composition and method for inhibiting yellowing of cured antistatic silicone rubber |
| JP5758845B2 (en) * | 2012-05-23 | 2015-08-05 | 信越化学工業株式会社 | Silicone rubber composition |
| JP5776650B2 (en) * | 2012-08-29 | 2015-09-09 | 信越化学工業株式会社 | Insulating silicone rubber composition |
| JP5462425B1 (en) * | 2012-11-05 | 2014-04-02 | モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社 | Thermosetting silicone rubber composition |
| KR102151512B1 (en) * | 2012-11-05 | 2020-09-03 | 모멘티브 파포만스 마테리아루즈 쟈판 고도가이샤 | Thermosetting silicone rubber composition |
| JP6688803B2 (en) * | 2015-02-16 | 2020-04-28 | ダウ・東レ株式会社 | Sponge forming silicone rubber composition and silicone rubber sponge |
| JP2017002218A (en) * | 2015-06-12 | 2017-01-05 | 信越化学工業株式会社 | High dielectric insulation silicone rubber composition |
| JP6497291B2 (en) * | 2015-10-14 | 2019-04-10 | 信越化学工業株式会社 | Insulating heat dissipation sheet |
| CN105219093A (en) * | 2015-11-04 | 2016-01-06 | 东莞星海丰电子有限公司 | A kind of silica gel product and preparation technology thereof |
| CN106893158A (en) * | 2017-04-20 | 2017-06-27 | 马鞍山市润启新材料科技有限公司 | A kind of environmental protection type antistatic insulating materials |
| JP2022517350A (en) | 2019-01-17 | 2022-03-08 | ダウ シリコーンズ コーポレーション | Antistatic silicone rubber composition |
| TW202035647A (en) | 2019-01-17 | 2020-10-01 | 美商陶氏有機矽公司 | Antistatic silicone rubber composition |
| WO2024053440A1 (en) * | 2022-09-05 | 2024-03-14 | 信越化学工業株式会社 | Thermally conductive millable silicone rubber composition and thermally conductive sheet |
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| CN1572835A (en) * | 2003-05-07 | 2005-02-02 | 信越化学工业株式会社 | Rubber composition for roller and ionic conductive rubber roller using the composition |
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| JP3036776B2 (en) * | 1990-02-27 | 2000-04-24 | 東レ・ダウコーニング・シリコーン株式会社 | Curable composition |
| JPH04103666A (en) * | 1990-08-23 | 1992-04-06 | Hokushin Ind Inc | Molded article of silicone rubber |
| JP3330771B2 (en) * | 1995-01-19 | 2002-09-30 | 三菱エンジニアリングプラスチックス株式会社 | Permanent antistatic polycarbonate resin composition |
| JP3115519B2 (en) * | 1995-05-15 | 2000-12-11 | 三洋化成工業株式会社 | Antistatic agent for silicone resin |
| JPH11199773A (en) * | 1997-12-24 | 1999-07-27 | E I Du Pont De Nemours & Co | Antistatic polymer composition and molded article thereof |
| JP3501055B2 (en) * | 1999-12-10 | 2004-02-23 | 信越化学工業株式会社 | Semiconductive silicone rubber composition and silicone rubber roll |
| KR20030060971A (en) * | 2000-12-07 | 2003-07-16 | 가네가후치 가가쿠 고교 가부시키가이샤 | Semiconductive Resin Composition and Semiconductive Member |
| JP4769924B2 (en) * | 2001-02-06 | 2011-09-07 | 三光化学工業株式会社 | High antistatic rubber composition |
| JP3766619B2 (en) * | 2001-08-30 | 2006-04-12 | 三光化学工業株式会社 | Antistatic composition, method for producing the same, and molded article using the same |
| JP2003082232A (en) * | 2001-09-07 | 2003-03-19 | Shin Etsu Chem Co Ltd | Silicone rubber composition for semiconductive roller and semiconductive roller |
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| CN1572835A (en) * | 2003-05-07 | 2005-02-02 | 信越化学工业株式会社 | Rubber composition for roller and ionic conductive rubber roller using the composition |
Also Published As
| Publication number | Publication date |
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| KR101295481B1 (en) | 2013-08-09 |
| KR20060092088A (en) | 2006-08-22 |
| TWI389978B (en) | 2013-03-21 |
| TW200639217A (en) | 2006-11-16 |
| CN1821309A (en) | 2006-08-23 |
| JP2006225422A (en) | 2006-08-31 |
| JP4905626B2 (en) | 2012-03-28 |
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