CN1693370A - Ionic conductor rubber composite and ionic conductor roller using the composite - Google Patents
Ionic conductor rubber composite and ionic conductor roller using the composite Download PDFInfo
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- CN1693370A CN1693370A CN 200510076270 CN200510076270A CN1693370A CN 1693370 A CN1693370 A CN 1693370A CN 200510076270 CN200510076270 CN 200510076270 CN 200510076270 A CN200510076270 A CN 200510076270A CN 1693370 A CN1693370 A CN 1693370A
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Abstract
The ionically conductive rubber composition comprises (A) an organopolysiloxane having in one molecule at least two alkenyl groups each bound to a silicon atom, (B) an organohydrogenpolysiloxane having in one molecule at least two hydrogen atoms each bound to a silicon atom and a polyether group via an alkylene linkage to a silicon atom, (C) a hydrosilylation catalyst, (D) an ionically conductive compound and (E) a phenolic antioxidant. The ionically conductive rubber roll comprises a core metal and an ionically conductive rubber layer consisting of the cured product of the above composition covering the circumference of the core metal.
Description
Technical field
The present invention relates to a kind of ionic conduction type rubber compositions of roller and similar products material for electrofax imaging device or similar device, and use the ionic conduction type roller of the composition.
Background technique
A kind of hydrosilylation reaction curable composition has been disclosed in (referenced patent document 1), and it includes polyethers, organic hydride polysiloxanes and platinum-type catalysts that alkenyl is had in the end of strand.In addition a kind of method for manufacturing ionic conduction type roller has also been disclosed in (referenced patent document 2), wherein solidify the composition prepared and the compound for assigning its electric conductivity is added in the rubber composition to addition-curable, thus a kind of ionic conduction type rubber layer that the exterior circumferential in roll shaft is formed is provided, wherein the composition includes to make polyoxyalkylene as main component, and it is solidified by hydrosilylation reactions.
However, synthesized cured product surface shows strong adhesion due to the poor compatibility of polyethers and organic hydride polysiloxanes, the problem of in addition there is also permeability over time.Therefore, it has proved that be difficult above-mentioned composition being used for roller under practical situation.
In addition, reagent in the case of assigning rubber electric conductivity, usually using p electron transfer type conductive material such as carbon black or carbon fiber as offer electric conductivity.However, it is known that if the pipe effect generated because of the structure of carbon means that electric current and voltage do not follow Ohm's law using conventional carbon black, and follow a kind of non-linear relation (with reference to non-patent literature 1).For for the roller around light-sensitive material, such as developer roll and transferring roller, it is not desirable to have the non-linear relation between this electric current and voltage, this just needs to carry out high-precision control to resistance.Various methods have been proposed to solve the problems, such as this, including phosphate (referenced patent document 3) is added, and have used potassium titanate crystal whisker (referenced patent document 4), but no one of these methods achieve satisfied effect.
[patent references 1] JP55-78055A
[patent references 2] JP7-300564A
[patent references 3] JP6-192486A
[patent references 4] JP8-120176
[non-patent reference 1] L.K.H.van Beekand and B.I.C.F.van Pul, J.Appl.Polymer Sci., 6,651 (1962)
Summary of the invention
Accordingly, the purpose of the present invention is to provide a kind of ionic conduction type rubber compositions, its rubber surface is not tacky or oil-tight, and resistance value shows minimum variation with alive variation is applied, and the rubber for preparation for electrofax imaging device or similar device in the middle of the roller is ideal.
Furthermore it is also an object that providing the ionic conduction type roller that a kind of exterior circumferential in roll shaft is surrounded with ionic conduction type rubber layer.
It conducts in-depth research to achieve the above object, as a result the inventors discovered that by introducing polyether structure in organic hydride polysiloxanes, then synthetic product and the organopolysiloxane containing alkenyl and phenolic-based antioxidant is compound, the surface adhesive (surface viscosity) of the cured product as made from the composition is obviously reduced, while also improving the permeability degree on the paper feeding of extension.Additionally, it was found that can also obtain good resistance stability by using the ionic conduction type compound when the voltage change of application, thus be achieved the present invention.
In other words, the present invention provides a kind of ionic conduction type rubber composition, it includes:
(A) organopolysiloxane for the alkenyl being bonded on silicon atom is contained at least two in per molecule,
(B) organic hydride polysiloxanes is bonded to the hydrogen atom on silicon atom and one by the polyether group on alkylene to silicon atom comprising at least two in per molecule, wherein
With respect to the alkenyl in 1 molar constituent (A), the molal quantity that the hydrogen atom on silicon atom is bonded in the component is 0.1-10 moles,
(C) a effective amount of hydrosilylation reaction catalyst,
(D) ionic conduction type compound, amount are 0.1-30 mass % relative to component (A) and component (B) quality sum, and
(E) phenolic-based antioxidant, amount are 0.1-15 mass % relative to component (A) and component (B) quality sum.
In addition, the present invention also provides a kind of ionic conduction type rollers comprising core, and ionic conduction type rubber layer being formed by the cured product of above-mentioned ionic conduction type rubber composition, being coated on core exterior circumferential.
Pass through the application present invention, a kind of ionic conduction type rubber composition can be obtained, its rubber surface is not tacky or oil-tight, with applying alive variation, resistance value shows minimum variation (voltage-dependent is minimum), and the rubber for preparing the roller being used in electrofax imaging device or similar device is ideal.
Detailed description of the invention
Fig. 1 is the layout for measuring the measuring device of present composition resistance value.
The detailed description of preferred embodiment
The following are the present invention to describe in more detail.In the present specification, term " polyether group " refers to the monoradical or structure that general formula as follows (1) represents:
-O(R2O)xR1 (1)
[wherein, R1Represent hydroxyl or alkyl, R2Group can be identical or different, and respectively represents alkylidene, and x represents the integer of two or more],
Or refer to the group or structure for the bivalent that general formula as follows (2) represent:
-O(R2O)x- (2)
[wherein, R2It is as defined above with x].Term " room temperature " means 25 DEG C.
[organopolysiloxane of (A) containing alkenyl]
Comprising at least two, preferably at least 3, the more preferable 4-10 alkenyls being bonded on silicon atom in organopolysiloxane (A) per molecule containing alkenyl, (A) is as the main component (matrix polymer) or crosslinking agent in the present composition.The number of alkenyl refers to the group average of many organosiloxanes containing alkenyl.If less than 2 group/molecules of alkenyl number being bonded on silicon atom, cured product becomes gel, it is meant that it cannot act as rubber.
Alkenyl typically contains 2-8, and preferably 2-6 is a, more preferable 2-3 carbon atom.Specific Exemplary alkenyl groups have vinyl, allyl, cyclobutenyl, pentenyl, hexenyl and heptenyl, but vinyl and allyl are preferred, and vinyl is especially desirable.These alkenyls can be bonded on the silicon atom of molecule chain end, and/or on the non-end silicon atom in strand.
In addition to alkenyl, the example of on the silicon atom that is equally bonded in component (A), replacing or non-substituted univalence hydrocarbyl typically comprises 1-12, preferably 1-8, more preferable 1-6 carbon atom.Specific example has the alkyl of such as methyl, ethyl, propyl, butyl, amyl, hexyl and heptyl etc；There is the aryl of such as phenyl, tolyl, xylyl and naphthalene；There is the aryl alkyl of such as benzyl and phenethyl etc；And such as chloromethyl, 3- chloropropyl and 3, the halogenated alkyl of 3,3- trifluoro propyls etc, and methyl therein, phenyl and 3,3,3- trifluoro propyls are that preferably, methyl and phenyl are particularly preferred.Particularly preferred polymer is at least 40 moles of %, preferably 40-98 moles of % that wherein methyl accounts for all organic groups (summations of i.e. all non-substituted or substituted univalence hydrocarbyls being bonded on silicon atom).If phenyl accounts for the 15-40 moles of % that be typically from of all organic groups, preferably 20-40 moles of % including phenyl.
The molecular structure of component (A) can be straight chain, the straight chain with part branch, cyclic structure, branch or tridimensional network.From the mechanical strength and elongation for obtaining good physical property such as cured product, and from the point of view of guaranteeing that composition has good processability, viscosity of the component (A) at 25 DEG C is preferably in 1-50000mPas, more preferable 2-10000mPas, most preferably 2-5000mPas.Moreover, the number of silicon atom is typically 2-1200, preferably 3-800 in the single molecule of the organopolysiloxane containing alkenyl of component (A), more preferable 4-500.
The specific example of the organopolysiloxane of the component (A) has 1, 3- divinyl -1, 1, 3, 3- tetramethyl disiloxane, 1, 3- dimethyl -1, 1, 3, 3- tetravinyl disiloxane, 1, 3, 5- trimethyl -1, 3, 5- trivinyl cyclotrisiloxane, 1, 3, 5, 7- tetramethyl -1, 3, 5, 7- tetravinyl cyclotetrasiloxane, 1, 3, 5, 7, 9- pentamethyl -1, 3, 5, 7, five vinyl cyclopentasiloxane of 9-, the copolymer of dimethyl siloxane and methyl vinyl silicone that copolymer molecule chain both ends trimethylsiloxy blocks, the methylvinyl-polysiloxane that strand both ends are blocked with trimethylsiloxy, the dimethyl siloxane that copolymer molecule chain both ends are blocked with trimethylsiloxy, methyl second The copolymer of alkenyl siloxane and methyl phenyl siloxane, the dimethyl polysiloxane that strand both ends are blocked with dimethylvinylsiloxy, the methylvinyl-polysiloxane that molecular weight both ends are blocked with dimethylvinylsiloxy, the copolymer of dimethyl siloxane and methyl vinyl silicone that copolymer molecule chain both ends dimethylvinylsiloxy blocks, the dimethyl siloxane that copolymer molecule chain both ends are blocked with dimethylvinylsiloxy, the copolymer of methyl vinyl silicone and methyl phenyl siloxane, the dimethyl siloxane that copolymer molecule chain both ends are blocked with dimethylvinylsiloxy, the copolymer of methyl vinyl silicone and diphenyl siloxane, the dimethyl siloxane and diphenyl siloxane that copolymer molecule chain both ends dimethylvinylsiloxy blocks Copolymer, strand both ends blocked with trivinyl siloxy dimethyl polysiloxane, by general formula R3 3SiO1/2Siloxane unit [wherein, the R of expression3For the alkyl of unsubstituted or substituted unit price above-mentioned, in addition to alkenyl.Below also apply this definition], general formula R3 2R4SiO1/2Siloxane unit [wherein, the R of expression4For alkenyl above-mentioned.Below also apply this definition], by general formula R3 2Siloxane unit that SiO is indicated and a small amount of by general formula SiO2Organopolysiloxane copolymers that the siloxane unit of expression is formed, by general formula R3 3SiO1/2Siloxane unit, the R of expression3 2R4SiO1/2The siloxane unit of expression and by general formula SiO2Organopolysiloxane copolymers that the siloxane unit of expression is formed, by general formula R3 2R4SiO1/2Siloxane unit, the general formula R of expression3 2The siloxane unit and a small amount of general formula SiO that SiO is indicated2Organopolysiloxane copolymers that the siloxane unit of expression is formed and by R3R4Siloxane unit, a small amount of general formula R of SiO expression3SiO3/2The siloxane unit or general formula R of expression4SiO3/2The organopolysiloxane copolymers that the siloxane unit of expression is formed.
Above-mentioned organopolysiloxane can be used as compounds combined use that single compound uses or two or more are different.
[the organic hydride polysiloxanes of (B) containing polyether group]
Comprising at least two hydrogen atom (i.e. general formula Si-H indicate hydrosilyl) on silicon atom is bonded in the organic hydride polysiloxanes per molecule of component (B) and by the polyether group on alkylene to silicon atom, and it is preferred that altogether molten (co-soluble) with component (A), polyether structure is introduced as main component (matrix polymer) or crosslinking agent, and in the cured product for preparing to composition of the invention.
The hydrogen atom number being bonded on silicon atom for including in per molecule is preferably 2-12, more preferable 2-8 atom.If the number of hydrogen atoms being bonded on silicon atom for including in per molecule is less than 2, the physical property of cured product, as mechanical strength and elongation are poor.Moreover, x is the integer of two or more, preferably the integer of 3-100, more preferably the integer of 3-50 in the above-mentioned general formula (1) for representing polyether group.
Component (B) can be prepared by reacting (b1) polymer (polyethers) and (b2) organic hydride polysiloxanes in the presence of hydrosilylation addition reaction catalyst, wherein (b1) per molecule includes at least one, it is preferred that 2-6 alkenyl, and the repetitive unit for forming main chain is oxyalkylene unit, it (b2) include at least two in per molecule, it is preferred that the 3-10 hydrogen atoms (Si -- H) being bonded on molecule chain end silicon atom and/or in strand on non-end silicon atom, its relative scale is so that the alkenyl in the hydrogen atom ratio (b1) being bonded on silicon atom in (b2) is excessive, so that the residual hydrogen atom number being bonded on silicon atom in addition reaction product per molecule is at least 2, it is preferred that 2-8.
The specific example of said components (b1) includes compound as described below, but the component is not limited to example shown below.
(in above-mentioned general formula, n, m and p respectively represent minimum 2 integer, preferably 2-500).
Single compound can be used in said components (b1), two or more different compounds can also be applied in combination, as long as the number for the remaining hydrogen atom being bonded on silicon atom in each molecule of above-mentioned addition reaction product is at least 2.
Other than hydrogen atom, the unsubstituted or substituted univalence hydrocarbyl on silicon atom being also bonded in component (b2) typically comprises 1-12, preferably 1-8, more preferable 1-6 carbon atom.Specific example includes the alkyl such as methyl, ethyl, propyl, butyl, amyl, hexyl and heptyl etc；There is the aryl of such as phenyl, tolyl, xylyl and naphthalene；There is the aryl alkyl of such as benzyl and phenethyl etc；And such as chloromethyl, 3- chloropropyl and 3, the halogenated alkyl of 3,3- trifluoro propyls etc, and wherein methyl, phenyl and 3,3,3- trifluoro propyls are preferred, and methyl and phenyl are particularly preferred.Organic hydride polysiloxane molecule structure can be straight chain, the straight chain with part branch, cyclic structure, branched chain or tridimensional network.Viscosity of the organic hydride polysiloxanes at 25 DEG C preferred 1-500mPas, more preferable 5-200mPas, most preferably 5-30mPas.Moreover, typically silicon atom number is 2-300, preferably 4-100, more preferable 4-0 in a molecule in component (b2).
The specific example of component (b2) has 1, 1, 3, 3- tetramethyl disiloxane, 1, 3, 5, 7- tetramethyl-ring tetrasiloxane, 1, 3, 5, 7, 9- pentamethyl cyclopentasiloxane, the methylhydrogen polysiloxanes that strand both ends are blocked with trimethylsiloxy, the dimethyl siloxane and methylhydrogensiloxane copolymer that copolymer molecule chain both ends trimethylsiloxy blocks, the dimethyl siloxane that copolymer molecule chain both ends are blocked with trimethylsiloxy, methylhydrogensiloxane and diphenylsiloxane copolymer, the methylhydrogensiloxane and diphenylsiloxane copolymer that copolymer molecule chain both ends trimethylsiloxy blocks, the dimethyl siloxane that copolymer molecule chain both ends are blocked with trimethylsiloxy, the copolymerization of methylhydrogensiloxane and methyl phenyl siloxane Methyl phenyl silicone that the dimethyl siloxane and methylhydrogensiloxane copolymer, the copolymer of the dimethyl siloxane that copolymer molecule chain both ends are blocked with dimethylhydridosiloxy and methyl phenyl siloxane, strand both ends that dimethyl polysiloxane that object, strand both ends are blocked with dimethylhydridosiloxy, copolymer molecule chain both ends are blocked with dimethylhydridosiloxy are blocked with dimethylhydridosiloxy, by general formula R3 3SiO1/2[wherein, R3For unsubstituted or substituted univalence hydrocarbyl above-mentioned.Below also apply this definition] indicate siloxane unit, by general formula R3 2HSiO1/2The siloxane unit of expression and a small amount of general formula SiO2The organopolysiloxane copolymers that the siloxane unit of representative is formed, by general formula R3 2HSiO1/2The siloxane unit of expression and a small amount of general formula SiO2The organopolysiloxane copolymers that the siloxane unit of representative is formed, and by general formula R3The siloxane unit and a small amount of general formula R that HSiO is indicated3SiO3/2Or general formula HSiO3/2The organopolysiloxane copolymers that the siloxane unit of expression is formed.Single compound can be used in the component (b2), and also can be used in combination two or more different compounds.
Component (B) specific example in the present invention, i.e. the addition reaction product of aforementioned component (b1) and (b2), including compound as follows, but component (B) is not limited to compound as follows.
In (including embodiment) described below, " Me " represents methyl, and " Ph " represents phenyl.
(wherein, in above-mentioned general formula n, m, p and q respectively represent minimum 2 integer and preferred 2-500).
Single compound can be used in organic hydride polysiloxanes, two or more compounds can also be applied in combination.
In the present compositions, the combined amount of component (B) should be enough to provide the hydrogen atom (Si-H) being largely bonded in component (B) on silicon atom, its content is 0.1-10 moles relative to the alkenyl in every 1 molar constituent (A), it is preferred that 0.5-5 moles, more preferable 0.5-3 moles.If the composition that the combined amount less than 0.1 mole, generates cannot sufficiently solidify, but if the numerical value is more than 10 moles, the heat resistance of cured product can significantly deteriorate.
[(C) hydrosilylation reaction catalyst]
The promotor (promotes) for the addition reaction being bonded between the hydrogen atom on silicon atom (Si -- H) in any alkenyl that can promote component (A) and component (B) can be used in component used in the present invention (C).Suitable example includes chloroplatinic acid, the modified chloroplatinic acid of alcohol, chloroplatinic acid and alkene, the complex of vinylsiloxane or acetylide, tetrakis triphenylphosphine palladium and three (triphenylphosphine) radium chlorides, but Platinum-based compounds, if vinylsiloxane complex is preferred.Single substance can be used in hydrosilylation reaction catalyst, or two or more different materials are used in combination.
The combined amount of component (C) is not particularly limited, any effective catalytic amount is sufficient, but the typical amount of the sum of catalytic metal atom quality relative composition (A) calculated, (B) constituent mass is 0.1-1000ppm, it is preferred that 1-500ppm, more preferable 10-100ppm.If the combined amount is too low, addition reaction obviously slows down, or solidification does not occur, and if combined amount is too many, the heat resistance of the cured product of synthesis is deteriorated.
[(D) ionic conduction type compound]
Component (D) in the present invention is used to assign ionic conductivity to gained cured product comprising the salt or (D-2) ionic liquid of (D-1) alkali or alkaline earth metal.Here term " ionic liquid " refers to the fuse salt under the fuse salt for liquid at room temperature, that is, known environment temperature, and refers in particular to the salt that its fusing point is no more than 50 DEG C and preferably -100~30 DEG C and more preferably -50~20 DEG C.The characteristic that such ionic liquid is shown includes the heat resistance of no vapour pressure (meaning its non-volatility) and height, and there are also non-combustible and chemical stabilities.
The salt example of component (D-1) alkali or alkaline earth metal includes the salt of alkali metal such as lithium, sodium and potassium etc and the salt of alkaline-earth metal such as calcium, barium, but preferred lithium salts.The specific example of these inorganic metal salts includes alkali metal salt such as LiClO4, LiCF3SO3, LiN (CF3SO2)2, LiAsF6, LiCl, NaSCN, KSCN, NaCl, NaI and KI and alkali salt such as Ca (ClO4)2、Ba(ClO4)2.Wherein, from the point of view of low resistance and satisfactory dissolubility are provided, LiClO4、LiCF3SO3、LiN(CF3SO2)2、LiAsF6And LiCl is preferred, and particularly preferred LiCF3SO3、LiN(CF3SO2)2。
The ionic liquid of component (D-2) includes doped quaternary ammonium salt cation and anion.The example of doped quaternary ammonium salt cation has imidazole salts and pyridinium ion and by general formula R5 4N+[wherein R5For hydrogen atom or have an organic group of 1-20 carbon atom] cation that represents.
In above-mentioned general formula, organic group R5Suitable example has the univalence hydrocarbyl and alkoxyalkyl of 1-20 carbon atom.Specific example has alkyl such as methyl, amyl, hexyl and heptyl；Aryl such as phenyl, tolyl, xylyl and naphthalene；Aryl alkyl such as benzyl and phenylethyl；Naphthenic base such as cyclopenta, cyclohexyl, cyclooctyl；Alkoxyalkyl such as ethoxyethyl group (- CH2CH2OCH2CH3).Moreover, R5The organic group of expression can also two be bonded together to form cyclic structure, in this case, two R5Group combines the organic group for forming a divalent.The hetero atom that the backbone portion of the bivalent group only can be formed by carbon atom, or also may include such as oxygen atom or nitrogen-atoms etc.Specific example has the bivalent hydrocarbon radical [alkylidene of Zhu Ruyou 3-10 carbon atom, and by general formula-(CH2)a-O-(CH2)bThe group that [wherein, a indicates the integer of 1-5, and b indicates the integer of 1-5, and a+b is the integer of 4-10] indicates].
Above-mentioned general formula R5 4N+The Cation examples of expression have-three n-octyl ammonium cation of methyl, ethoxyethyl group crassitude cation and ethoxyethyl group methyl morpholine cation.
Above-mentioned anion is not particularly limited, but anion preferably has AlCl4 -、Al3Cl8 -、Al2Cl7 -、ClO4 -、PF6 -、BF4 -、CF3SO3 -、(CF3SO2)2N-、(CF3SO2)3C-, wherein particularly preferred PF6 -、BF4 -、CF3SO3 -(CF3SO2)2N-。
The specific example of ionic liquid comprising quaternary ammonium cation and anion includes bis- (fluoroform sulphonyl) imines of-three n-octyl ammonium of methyl, bis- (fluoroform sulphonyl) imines of ethoxyethyl group crassitude, is represented by general structure as follows:
And bis- (fluoroform sulphonyl) imines of ethoxyethyl group methyl morpholine, what general structure as follows represented:
Ionic conduction type compound can be used alone or two or more different compound combinations use.
The combined amount of component (D) is typically the 0.1-30 mass % of component (A) and (B) quality summation, and preferably 0.5-20 mass %, more preferable 1-15 mass %.If the amount cannot obtain the 10 of target less than 0.1 mass %4-108Ohm resistance can generate cost problem but if the amount is greater than 30 mass %.
[(E) phenolic-based antioxidant]
Component (E) is phenolic-based antioxidant, the specific example of suitable compound includes 2,6- di-t-butyl-paracresol, 2,2 '-di-2-ethylhexylphosphine oxides (- 6 tert-butyl phenol of 4- methyl), 4,4 '-thiobis (3- methyl-t-butyl phenol), 1,1,3- tri- (2- methyl -4- hydroxyl -5- tert-butyl-phenyl) butane, [3- (3 of pentaerythrite four, 5- di-tert-butyl-hydroxy phenyl) propionic ester], octadecyl alcolol -3- (3,5- di-tert-butyl-hydroxy phenyl) propionic ester and tocopherol.The phenolic-based antioxidant can be used alone or two or more different compound combinations use.
The additional amount of component (E) is typically the 0.1-15 mass % of component (A) and (B) quality summation, and preferably 0.5-10 mass %, more preferable 1-8 mass %.If the amount less than 0.1 mass %, is difficult to obtain the antioxidant effect of target, but if the amount is greater than 15 mass %, antioxidant effect, which is not observed, further to be improved.
[other optional components]
In addition to said components (A)-(E), if desired, other optional components such as reaction controlling agent, inorganic filler, heat resistance imparting agent, anti-flammability imparting agent, thixotropy conferring agents, pigment, dyestuff, silicone rubber powder and silicone powders can also be added in composition of the invention.
Reaction controlling agent-
Reaction controlling agent is that is promoted addition reaction catalyst solidified the compound of inhibiting effect, and conventional reaction controlling agent can be used.The suitable specific example of reaction controlling agent includes phosphorus-containing compound such as triphenyl phosphite and triphenylphosphine；Nitrogenous compound such as tri-n-butylamine, tetramethylethylenediamine and benzotriazole；Sulfur-containing compound such as autumn blue female single sulfide and tetramethylene sulfoxide；The acetylene compound such as 3- methyl-1-pure and mild 1- ethynylcyclohexanol of butyl- 3-；Compound containing at least two alkenyl such as methyl ethylene cyclotetrasiloxane and Triallyl isocyanurate；Hydroperoxides such as methyl ethyl ketone hydroperoxides and cumene hydroperoxide；And maleic acid derivatives such as dimethyl maleate and diallyl maleate.
The reaction controlling agent shows that the effect on solidifying is rather depending on the chemical structure of reaction controlling agent.Accordingly, the combined amount of reaction controlling agent must be adjusted to most suitable amount according to the specific reaction controlling agent used, and a kind of general preferred scope cannot be provided by meaning.However, if the combined amount is too small, it is difficult to which the long term storage stability obtained at room temperature then solidifies in itself but if combined amount is too big and will receive inhibition.
Inorganic filler-
It is previously described for the inorganic filler of enhancing product composition, and is typically used in any filler of conventional silicone rubber composition and all can be used.Specific example has fumed silica, crystalline silica, precipitated silica, hollow filler, silsesquioxane, fumedization titanium, magnesia, zinc oxide, iron oxide, aluminium hydroxide, magnesium carbonate, calcium carbonate, zinc carbonate, stratiform mica, diatomite and glass fibre, or the filler for the above-mentioned type for carrying out hydrophobic treatment to its surface with organo-silicon compound such as organoalkoxysilane compounds, organochlorosilane compound, organosilazanes or low-molecular-weight siloxane compound that can choose.In view of the reinforcing effect to be obtained, fumed silica, precipitated silica BET specific surface area be 50-500 meters squared per gram, preferably 100-400 meters squared per gram.
The specific example of above-mentioned inorganic filler, it is enumerated by brand name, including hydrophily silica product such as Aerosil 130,200 and 300 (Nippon Aerosil Co., Ltd. manufactured with Degussa AG), CabosilMS-5 and MS-7 (manufacture of Cabot company), Rheorosil QS-102 and 103 (manufactures of Tokuyama company), and Nipsil LP (manufacture of Nippon Silica Industry Co., Ltd.)；Hydrophobic silica silicon product such as Aerosil R-812, R-812S, R-972 and R-974 (Degussa AG manufacture), Rheorosil MI-10 (manufacture of Tokuyama company) and Nipsil SS are serial (manufacture of Nippon SilicaIndustry Co., Ltd.)；And crystalline silica product such as crystallite, Minusil and Imisil.
Heat resistance imparting agent-
The example of above-mentioned heat resistance imparting agent has cerium oxide, cerium hydroxide, iron oxide red and titanium oxide.
[ionic conduction roller]
The above-mentioned present composition can be used as the roller material of such as electrofax imaging device or similar device.Specifically, the composition can be provided in around the photosensitive body of electrofax printer, duplicator or facsimile machine or similar products, be used for feed roller, developing roll, toner supply roller or transfer roller.The example of these ionic conduction rollers includes ionic conduction roller, and it includes core and ionic conduction rubber layer, which is formed by the cured product of above-mentioned ionic conduction rubber composition, is coated on the exterior circumferential of core.Conventional method and proper step example for manufacturing such ion roller is disclosed directly below.Explanation concentrates on a kind of liquid, addition curing rubber composition below, represents a preferred embodiment of the present invention.
Firstly, being mixed each component of the predetermined amount of 2- liquid rubber composition with static mixer, or the rotary screw of the rubber composition each component dynamic mixer is mixed.Then obtained mixture is injected into the molding for being used for forming roller, it includes the fixation metal cores for having been subjected to priming coat process.Then, the rubber composition of hot injection and make its solidification, thus form rubber layer in the exterior circumferential of metal core, then take out roller from molding.Then, if it is desired, the surface of rubber layer can coat fluorine-based coating agent, urethane groups coating agent, polyamide-based coating agent or amino silicone alkyl coating agent.
In addition, each component of the predetermined amount of 2- liquid rubber composition is mixed with static mixer, or the rotary screw of the rubber composition each component dynamic mixer is mixed in another manufacturing method.Then obtained mixture is injected into the molding for being used for forming roller, it includes the fixation metal cores for having been subjected to priming coat process.Then, thus the rubber composition of hot injection and solidification form rubber layer in the exterior circumferential of metal core, then take out roller from molding, and polish to the surface of roller.Then, if it is desired, the surface of rubber layer can coat fluorine-based coating agent, urethane groups coating agent, polyamide-based coating agent or amino silicone alkyl coating agent.
A variety of different materials can be used for manufacturing the metal core of roller in the present invention, such as iron, aluminium and stainless steel.Also, the metal core for having been subjected to priming coat process also can be used.
Specific embodiment
Embodiment
Below with a series of embodiments come the present invention is described in detail, but the present invention is in no way limited to only these embodiments.In these embodiments, viscosity number refers to the numerical value measured at 25 DEG C.
<synthetic example 1>
Be equipped with stirring rod, titration slot, thermometer and cooling tube flask in the polypropylene oxide of (b1) 100 grams of both ends allyl cappeds is added, by following general structure represented by:
(b2) 27 gram 1,3,5,7- tetramethyl-ring tetrasiloxanes and 80 grams of toluene.The flask is heated to 65-70 DEG C, 0.1 gram of chloroplatinic acid-vinylsiloxane complex compound (platinum content: 0.5 mass %) then is added into toluene solution.Then in being reacted 3 hours at 70 DEG C, toluene and excessive 1,3,5,7- tetramethyl-ring tetrasiloxane are removed at 80 DEG C, 2kPa, thus generated by the compound G-1 of general structure expression shown below:
Its viscosity is 3.9Pas, and hydrogen atom content is 0.13 mass %.
<synthetic example 2>
In addition to by 100 grams of one end allyl cappeds of the polypropylene oxide of (b1) 100 grams of both ends allyl cappeds in synthetic example 1, replaced by the polyethylene oxide represented by following general structure,
And by (b2) 1,3,5,7- tetramethyl-ring tetrasiloxanes are increased to except 80 grams by 27 grams, are reacted by with the identical mode of synthetic example 1, and the compound G-1 indicated by general structure shown below is generated:
Its viscosity is 0.35Pas, and hydrogen atom content is 0.44 mass %.
[embodiment 1]
By by (A) 11 mass parts 1, 3, 5, 7- tetramethyl -1, 3, 5, 7- tetravinyl cyclotetrasiloxane, (B) 100 mass part compound G-1 (so that the vinyl of the relatively each molar constituent (A) of the molal quantity of the Si -- H in component (B) is about 1.0 moles), (C) 2 mass parts chloroplatinic acids-vinylsiloxane complex compound (platinum content: 0.5 mass %), 0.3 mass parts 1- ethynylcyclohexanol, (D) bis- (fluoroform sulphonyl) imines (the 1.8 mass % for being equivalent to component (A) and (B) summation) of 2 mass parts lithiums and four [3- (3 of (E) 5 mass parts pentaerythrite, 5- di-tert-butyl-hydroxy phenyl) propionic ester] (the 4.5 mass % for being equivalent to component (A) and (B) summation) uniformly mixed It is combined and prepares composition 1.Heating the composition 1 of above-mentioned acquisition at 120 DEG C makes its solidification for 10 minutes, generates cured product 1, hardness 40.The laminar cured product of the hardness being measured as by preparing 6 millimeters thicks is overlapped 2 layers of sheet material, then measures hardness with Asker-C hardometer (below also using this method) as test specimens.
[embodiment 2]
In addition to replacing bis- (fluoroform sulphonyl) imines of (D) 2 mass parts lithium in embodiment 1 with bis- (fluoroform sulphonyl) imines (the 9.0 mass % for being equivalent to component (A) and (B) summation) of 10 mass parts ethoxyethyl group crassitudes, composition 2 is prepared in the same manner as example 1.The heating of combinations of the above object 2 is made into its solidification for 10 minutes at 120 DEG C, generates cured product 2, hardness 40.
[embodiment 3]
By including 6.7 moles of %CH by (A) 100 mass parts2=CH (CH3)2SiO1/2Unit, 63.3 moles of % (CH3)2SiO unit and 30 moles of % (C6H5)2The viscosity of SiO unit is the organopolysiloxane of 0.7Pas, (B) 43 mass part compound G-1 (so that the vinyl of the relatively each molar constituent (A) of the molal quantity of component (B) Si -- H is about 1.0 moles), 0.25 mass parts 1- ethynylcyclohexanol, (C) 2 mass parts chloroplatinic acids-vinylsiloxane complex compound (platinum content: 0.5 mass %), (D) bis- (fluoroform sulphonyl) imines (the 1.4 mass % for being equivalent to component (A) and (B) summation) of 2 mass parts lithiums and (E) 1 mass parts octadecyl alcolol -3- (3, 5- di-tert-butyl-hydroxy phenyl) propionic ester (the 0.7 mass % for being equivalent to component (A) and (B) summation) is homogenously mixed together and prepares composition 3.The heating of combinations of the above object 3 is made into its solidification for 10 minutes at 120 DEG C, generates cured product 3, hardness 17.
[embodiment 4]
By by (A) 24.4 mass parts 1, 3, 5, 7- tetramethyl -1, 3, 5, 7- tetravinyl cyclotetrasiloxane, (B) 50 mass part compound G-1 and (B) 50 mass part compound G-2 (so that the vinyl of the relatively each molar constituent (A) of the total mole number of Si -- H in compound G-1 and G-2 is about 1 mole), (C) 2 mass parts chloroplatinic acids-vinylsiloxane complex compound (platinum content: 0.5 mass %), (D) bis- (fluoroform sulphonyl) imines (the 4.0 mass % for being equivalent to component (A) and (B) summation) of-three n-octyl ammonium of 5 mass parts methyl and (E) 1 mass parts tocopherol (the 0.8 mass % for being equivalent to component (A) and (B) summation) are homogenously mixed together and prepare composition 4.The heating of combinations of the above object 4 is made into its solidification for 10 minutes at 120 DEG C, generates cured product 4, hardness 80.
[comparative example 1]
By by the polypropylene oxide (average degree of polymerization 90) of (A) 100 mass parts both ends as described in synthetic example 1 allyl capped, (B) 30 mass part compound G-1 (so that the vinyl of the relatively each molar constituent (A) of the molal quantity of component (B) Si -- H is about 1 mole) and (C) 2 mass parts chloroplatinic acid-vinylsiloxane complex compound (platinum content: 0.5 mass %).Heating the composition C1 of above-mentioned acquisition at 120 DEG C makes its solidification for 10 minutes, generates cured product C1, hardness 12.The cured product shows the surface viscosity of height.
[comparative example 2]
Except not using component (E) pentaerythrite four [3- (3,5- di-tert-butyl-hydroxy phenyl) propionic ester], composition C2 is prepared by mode same as Example 1.Combinations of the above object C2 heating is made into its solidification for 10 minutes at 120 DEG C, generates cured product C2, hardness 40.
<test method>
Sample for test surfaces viscosity and permeability characteristic is prepared: by the way that rubber composition 1-4, C1 and C2 to be injected into molding respectively, then the temperature to 120 DEG C and is kept 10 minutes come compression molding the composition by heating mould, sheet curing rubber sample 1-4, C1 and C2,29 millimeters of diameter, 12.5 millimeters of thickness is consequently formed.Sample for measuring resistance is also prepared in the same way, and only thickness reduces to 6 millimeters.With these samples according to testing standard below measurement surface viscosity, permeability presence or absence and resistance value.As a result it is shown in Table 1.
[test item]
1. surface viscosity
Then curing rubber sample is kept the state 72 hours by 25% compression at 70 DEG C, then touched by finger and determine surface viscosity presence or absence.Evaluation result in the following manner.
A: do not discover viscosity
B: slight viscosity can be discovered
C: apparent viscosity can be discovered
2. permeability
Then curing rubber sample is kept the state 72 hours by 25% compression at 70 DEG C, then observe by the naked eye whether determining specimen surface has permeability.Evaluation result in the following manner.
A: do not discover permeability
B: slight permeability can be discovered
C: apparent permeability can be discovered
3. resistance value
As shown in Figure 1, curing rubber sample 1 is clipped between electrode 2 and core 3, the then resistance value between measuring electrode 2 and core 3.Electrode 2 includes 2 pole pieces, and electrode is switched by switching relay 5, is measured the resistance of A single sample two positions, is then determined its average value.With ultra-high resistance meter 4 (brand name: R8340, Advantest company manufacture) measurement resistance value.Resistance value measures under the voltage of 1V and 100V, is thus capable of measuring resistance value with respect to the variation (voltage-dependent) that voltage changes.
[table 1]
|
|
|
| Embodiment 4 | Comparative example 1 | Comparative example 2 | ||
| Original state | Surface viscosity | A | A | A | A | C | A |
| Permeability | A | A | A | A | A | A | |
| After 72 hours (70 DEG C) | Surface viscosity | A | A | A | A | C | B |
| Permeability | A | A | A | A | C | B | |
| Resistance value (ohm centimetre) | 1V | 2.3×107 | 9.5×108 | 2.3×107 | 5.2×108 | 6.4×107 | 2.7×107 |
| 100V | 1.6×107 | 5.4×108 | 1.3×107 | 4.9×108 | 2.3×107 | 2.0×107 |
<evaluation>
The composition of embodiment 1-4 meets requirement of the invention, and surface does not show viscosity and permeability, and resistance value is varied less with respect to what voltage changed.On the contrary, the composition of comparative example 1 is free of ionic conduction type compound (D), is also free of the phenolic-based antioxidant of component (E), show perceptible surface viscosity in its initial state, and cured product shows surface viscosity and permeability after being kept for 72 hours at 70 DEG C.In addition, resistance value is also larger with respect to the variation that voltage changes.The composition of comparative example 2, is free of the phenolic antioxidant of component (E), and cured product shows surface viscosity and permeability after being kept for 72 hours at 70 DEG C.
[industrial applicibility]
It is expected that the ionic conduction roller comprising ionic conduction type composition of the invention may be used to provide around the photosensitive body in electrofax imaging device such as electrofax printer, duplicator, as the material for forming feed roller, developing roll, toner supply roller or transfer roller etc..
Claims (4)
1. ionic conduction type rubber composition, it includes:
(A) per molecule includes the organopolysiloxane that at least two is bonded to the alkenyl group on silicon atom,
(B) per molecule includes the organic hydride polysiloxanes of the hydrogen atom that is bonded on silicon atom of at least two and the polyether group being bonded on silicon atom by alkylene bond, wherein with respect to the alkenyl in 1 mole of component (A), the molal quantity for being bonded to the hydrogen atom on silicon atom is 0.1-10 moles
(C) a effective amount of hydrosilylation reaction catalyst,
(D) ionic conduction type compound, in an amount equivalent to the 0.1-30 mass % of the component (A) and the component (B) quality summation, and
(E) phenol-based anti-oxidants, in an amount equivalent to the 0.1-15 mass % for the component (A) and the component (B) quality summation.
2. ionic conduction type rubber composition according to claim 1, wherein the ionic conduction type compound of the component (D) is the salt of alkali or alkaline earth metal.
3. ionic conduction type rubber composition according to claim 1, wherein the ionic conduction type compound of the component (D) is ionic liquid.
4. ionic conduction type rubber rollers, it includes cores and ionic conduction type rubber layer, which is obtained by the cured product of ionic conduction type rubber composition as claimed in any one of claims 1-3, and is covered on the exterior circumferential of the core.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP139167/04 | 2004-05-07 | ||
| JP2004139167 | 2004-05-07 |
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|---|---|
| CN1693370A true CN1693370A (en) | 2005-11-09 |
| CN100471903C CN100471903C (en) | 2009-03-25 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB2005100762701A Active CN100471903C (en) | 2004-05-07 | 2005-04-30 | Ionic conductor rubber composite and ionic conductor roller using the composite |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101910317B (en) * | 2007-12-27 | 2012-08-08 | 迈图高新材料日本合同公司 | Thermosetting silicone rubber compound composition |
| CN101910316B (en) * | 2007-12-27 | 2013-09-11 | 迈图高新材料日本合同公司 | Thermosetting silicone rubber composition |
| CN103421323A (en) * | 2012-05-22 | 2013-12-04 | 信越化学工业株式会社 | Antistatic silicone rubber composition and a silicone rubber antistatic inhibiting yellowing of the cured method |
| CN103998992A (en) * | 2011-12-19 | 2014-08-20 | 佳能株式会社 | Electrically conducting member for electrophotography, process cartridge and electrophotographic image forming apparatus |
| CN106349707A (en) * | 2016-08-19 | 2017-01-25 | 深圳市乐普泰科技股份有限公司 | Conductive silicone rubber, conductive rubber-covered roller and production method of conductive rubber-covered roller |
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2005
- 2005-04-30 CN CNB2005100762701A patent/CN100471903C/en active Active
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101910317B (en) * | 2007-12-27 | 2012-08-08 | 迈图高新材料日本合同公司 | Thermosetting silicone rubber compound composition |
| CN101910316B (en) * | 2007-12-27 | 2013-09-11 | 迈图高新材料日本合同公司 | Thermosetting silicone rubber composition |
| CN103998992A (en) * | 2011-12-19 | 2014-08-20 | 佳能株式会社 | Electrically conducting member for electrophotography, process cartridge and electrophotographic image forming apparatus |
| CN103998992B (en) * | 2011-12-19 | 2016-03-30 | 佳能株式会社 | Conductive member for electrophotography, handle box and electrophotographic image-forming apparatus |
| CN103421323A (en) * | 2012-05-22 | 2013-12-04 | 信越化学工业株式会社 | Antistatic silicone rubber composition and a silicone rubber antistatic inhibiting yellowing of the cured method |
| CN103421323B (en) * | 2012-05-22 | 2018-01-23 | 信越化学工业株式会社 | The method of the xanthochromia of Antistatic silicone rubber composition and suppression antistatic behaviour silicon rubber solidfied material |
| CN106349707A (en) * | 2016-08-19 | 2017-01-25 | 深圳市乐普泰科技股份有限公司 | Conductive silicone rubber, conductive rubber-covered roller and production method of conductive rubber-covered roller |
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