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CN101276167A - Method for preparing semiconductive silicone rubber components for electrophotographic apparatus, and roll and belt for electrophotographic apparatus having the silicone rubber components - Google Patents

Method for preparing semiconductive silicone rubber components for electrophotographic apparatus, and roll and belt for electrophotographic apparatus having the silicone rubber components Download PDF

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Publication number
CN101276167A
CN101276167A CNA2008100019731A CN200810001973A CN101276167A CN 101276167 A CN101276167 A CN 101276167A CN A2008100019731 A CNA2008100019731 A CN A2008100019731A CN 200810001973 A CN200810001973 A CN 200810001973A CN 101276167 A CN101276167 A CN 101276167A
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China
Prior art keywords
electrostatic printing
printing apparatus
base material
roller
layer
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Chinese (zh)
Inventor
平林佐太央
中村勉
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Shin Etsu Chemical Co Ltd
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Shin Etsu Chemical Co Ltd
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Publication of CN101276167A publication Critical patent/CN101276167A/en
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G5/00Recording members for original recording by exposure, e.g. to light, to heat, to electrons; Manufacture thereof; Selection of materials therefor
    • G03G5/02Charge-receiving layers
    • G03G5/04Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
    • G03G5/05Organic bonding materials; Methods for coating a substrate with a photoconductive layer; Inert supplements for use in photoconductive layers
    • G03G5/0528Macromolecular bonding materials
    • G03G5/0557Macromolecular bonding materials obtained otherwise than by reactions only involving carbon-to-carbon unsatured bonds
    • G03G5/0578Polycondensates comprising silicon atoms in the main chain
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G15/00Apparatus for electrographic processes using a charge pattern
    • G03G15/06Apparatus for electrographic processes using a charge pattern for developing
    • G03G15/08Apparatus for electrographic processes using a charge pattern for developing using a solid developer, e.g. powder developer
    • G03G15/0806Apparatus for electrographic processes using a charge pattern for developing using a solid developer, e.g. powder developer on a donor element, e.g. belt, roller
    • G03G15/0818Apparatus for electrographic processes using a charge pattern for developing using a solid developer, e.g. powder developer on a donor element, e.g. belt, roller characterised by the structure of the donor member, e.g. surface properties
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G15/00Apparatus for electrographic processes using a charge pattern
    • G03G15/20Apparatus for electrographic processes using a charge pattern for fixing, e.g. by using heat
    • G03G15/2003Apparatus for electrographic processes using a charge pattern for fixing, e.g. by using heat using heat
    • G03G15/2014Apparatus for electrographic processes using a charge pattern for fixing, e.g. by using heat using heat using contact heat
    • G03G15/2053Structural details of heat elements, e.g. structure of roller or belt, eddy current, induction heating
    • G03G15/2057Structural details of heat elements, e.g. structure of roller or belt, eddy current, induction heating relating to the chemical composition of the heat element and layers thereof
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G2215/00Apparatus for electrophotographic processes
    • G03G2215/20Details of the fixing device or porcess
    • G03G2215/2003Structural features of the fixing device
    • G03G2215/2048Surface layer material
    • G03G2215/2051Silicone rubber

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Electrophotography Configuration And Component (AREA)
  • Dry Development In Electrophotography (AREA)
  • Cleaning In Electrography (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
  • Fixing For Electrophotography (AREA)
  • Rolls And Other Rotary Bodies (AREA)

Abstract

The invention relates to a preparation method of an electrostatic printing device semiconductor silicone rubber component, and electrostatic printing device revolve and belt which comprise the silicone rubber component. The method can prepare the electrostatic printing device silicone rubber component in which low molecular weight siloxane component number is greatly reduced. The method comprises following steps: forming molded bituminized product via molding and bituminizing a silicone rubber compound which comprises following components: (A) 100 phr organic based polysiloxane expressed by following average composition general formula (1): (wherein, R represents substituted or non-substituted monovalent hydrocarbon radical, and n represents the number in the range of 1.95 to 2.05), and (B) conductivity endowing agent with enough amount for endowing semi-conduction, and (C) curing agent with enough amount for solidifying the component (A); and processing the molded bituminized product in the pressure not more than 5.0*10<4>Pa and in the temperature of 80 Deg C to 180 Deg C.

Description

The electrostatic printing apparatus preparation method of semiconductor silicon rubber component, and the electrostatic printing apparatus roller and the band that contain them
Technical field
The present invention relates to the silicone member that electrostatic printing apparatus (electrophotographic device) is made with the preparation method of semiconductor silicon rubber component, with this method, and the electrostatic printing apparatus usefulness roller and the band that contain this silicone member.
Background technology
Silicon rubber is used as the structured material that the used OPC of electrostatic printing apparatus (for example duplicating machine, facsimile recorder and printer) (organic photoconductor (organic photoconductor)) that is arranged in the employing electrostatic printing method rouses various rollers on every side (for example developer roll, toner (toner) are carried sponge roller, cleaning sponge roller and fixing roller) or various band (for example strip-like developing pipe and photographic fixing band).
Silicone member often comprises a small amount of uncrosslinked low-molecular-weight siloxane component, and they are present in the organopolysiloxane (organopolysiloxanes) as silicone rubber material.If these low-molecular-weight siloxane components are moved on OPC drum or the toner from silicone member, will cause such as the leukorrhea of printed images or fuzzy defective.A kind of example of known method of the low-molecular-weight siloxane component migration that suppresses these types relates to the extremely low material of the content of this low-molecular-weight siloxane as the raw material organopolysiloxane, add the silicon rubber powder that the low-molecular-weight siloxane fraction is reduced already then, thereby reduce the amount (referring to patent documentation 1) of low-molecular-weight siloxane in the prepared silicone member.In addition, also proposed low-molecular-weight siloxane is adsorbed on the filler, thereby avoided these low-molecular-weight siloxanes to move out of silicone member and stick to method (referring to patent documentation 2) on other members.
Silicon rubber often needs to heat-treat, to realize secondary cross-linking.Under addition-crosslinked situation, this heat treated purpose is to improve the production rate that is used as the aliphatic unsaturated group (for example vinyl) that connects on the organopolysiloxane main chain of base polymer and is used as silicon ethylidene (silethylene) key of addition reaction (hydrosilylation) generation between the organic hydrogen polysiloxanes of crosslinking chemical, thereby improves the compression set of product rubber.Under the crosslinked situation of organic peroxide, thermal treatment can be removed the organic peroxide that produces during the heat curing and be decomposed residue, can also avoid variable color.In addition, under the situation of sponge foams layered product, need thermal treatment to remove the decomposition residue of gas-development agent, and the interior pressure in the balance foamed products, thereby improve the dimensional stability of foamed products.In addition, heat treated another purpose of the crosslinked all frequent employing of addition-crosslinked and organic peroxide is to reduce the quantity of low-molecular-weight siloxane component.The minimizing of this low-molecular-weight siloxane fraction is not only for the image deflects of avoiding the above-mentioned type, and for contact fault that suppresses the switch place or the like and to improve the dimensional stability of layered product all very important.
The temperature conditions of secondary cross-linking is generally according to the decomposition temperature of the material of preparing volatilization and removing, and the vapour pressure of these target materials under treatment temperature determined.Temperature often is set in the temperature that approaches the silicon rubber heat-resisting upper temperature limit.The secondary cross-linking condition of reporting in the document often is recommended in 200 ℃ of 4 hours (referring to patent documentations 3) of heating down.So the reason of recommending is, if secondary cross-linking is carrying out above under 200 ℃ the temperature, thermal degradation causes the Si-O key in the silicon rubber to disconnect so, and the phenomenon that causes low-molecular-weight siloxane to produce just becomes obvious especially.
Yet, since low-molecular-weight siloxane ooze out silicone member and move to OPC drum or toner on be infected with (staining) and the still not fully solution of image deflects problem in the electrostatic printing apparatus that causes, still need further improvement.
[patent documentation 1] JP 2748215 B2
[patent documentation 2] JP 3324413 B2
[patent documentation 3] " Silicone Handbook ", Kunio Ito edits, Nikkon KogyoShimbun, Ltd. publishes, August 31 nineteen ninety, the 326th page and 612 pages.
Summary of the invention
[the problem to be solved in the present invention]
Therefore, the purpose of this invention is to provide the improved method for preparing silicone member, this method can prepare the electrostatic printing apparatus silicone member that the amount of low-molecular-weight siloxane component significantly is reduced.
The inventor passes through the further investigation of the secondary cross-linking treatment conditions of silicon rubber is found, though one of fundamental purpose of carrying out secondary cross-linking is to reduce once the quantity of the low-molecular-weight siloxane component that exists in the silicon rubber of crosslinked back, therefore and make the secondary cross-linking temperature in being no more than 200 ℃ temperature range, set highly as far as possible, but in fact these conditions can cause the fracture in the organopolysiloxane main chain, thereby in fact promote the generation of low-molecular-weight siloxane.Therefore, by the further research to the secondary cross-linking condition, the inventor can find preparation method of the present invention.
In other words,, the invention provides the preparation method of electrostatic printing apparatus, may further comprise the steps with the semiconductor silicon rubber component in order to realize above purpose:
The rubber composition that comprises following component by molding on base material solidifies the cured article that said composition obtains molding then:
(A) 100 mass parts are by the following average organopolysiloxane of forming general formula (1) expression:
R nSiO (4-n)/2 (1)
(wherein the R representative replaces or unsubstituted monovalence alkyl, and n represents the number of 1.95-2.05),
(B) the electric conductivity imparting agent of q.s, with give semiconduction and
(C) hardening agent of q.s, with energy curing component (A),
Wherein between base material and rubber composition, can be provided with or not be provided with the middle layer; With
Be no more than 5.0 * 10 4Handle the cured article of resulting molding under the pressure of Pa and 80-180 ℃ the temperature.
[effect of the present invention]
Preparation method of the present invention can effectively remove the free silicone oil components such as low-molecular-weight siloxane and oligomer, and suppresses the thermal degradation of siloxane polymer during the secondary cross-linking.The gained silicone member contains the free silicone oil components of these types of remarkable reduction, thereby when adopting this silicone member in the electrostatic printing apparatus,, sharply reduces silicone components because moving to the appearance such as leukorrhea or fuzzy image deflects that causes on the bulging or toner of OPC.
Owing to contain the low-molecular-weight siloxane component of remarkable reduction with the silicone member of preparation method's acquisition of the present invention; thereby reduced being infected with of OPC drum, or making to be commonly used at the various of this countermeasure of being infected with is infected with diaphragm such as polyurethane coating or can reduces thickness and can remove fully.
Embodiment
More detailed description of the present invention is provided below.
[electrostatic printing apparatus semiconductor silicon rubber component]
Electrostatic printing apparatus is to adopt electrostatic printing method to carry out the device of Flame Image Process, and the example of this device comprises duplicating machine, facsimile recorder and printer.
Electrostatic printing apparatus according to the present invention is meant especially that with the semiconductor silicon rubber component electrostatic printing apparatus duration of work is set to the member that directly or indirectly contacts with OPC drum or toner.The representative instance of this silicone member comprises the member that is used to make up electrostatic printing apparatus roller or electrostatic printing apparatus band.
In the present invention, the electrostatic printing apparatus roller comprises the roller core rod, and the semiconductor silicon of one deck at least rubber layer that provides on the mandrel outer perimeter surface (example of semiconductor silicon rubber component), can arrange or not arrange the middle layer between plug and rubber layer.The example of these electrostatic printing apparatus rollers comprises developer roll, toner conveying sponge roller, cleaning sponge roller and fixing roller.
In the present invention, the electrostatic printing apparatus band comprises the base material of belt shape, and the silastic-layer of one deck at least that provides at the base material top (example of semiconductor silicon rubber component), can arrange or not arrange the middle layer between base material and rubber layer.The example of these electrostatic printing apparatus bands comprises strip-like developing pipe and photographic fixing band.
[rubber composition]
The rubber composition that is used for preparation method of the present invention is at first described.In the following description, except as otherwise noted, " part " all refers to " mass parts ".
-(A) organopolysiloxane-
The organopolysiloxane of component (A) becomes general formula (1) expression with following average group.
R nSiO (4-n)/2 (1)
Form in the general formula (1) average, the replacement of R representative or the example of unsubstituted monovalence alkyl comprise the alkyl such as methyl, ethyl, propyl group, butyl, hexyl or dodecyl, naphthenic base such as cyclohexyl, alkenyl such as vinyl, allyl, butenyl group or hexenyl, aryl such as phenyl or tolyl, aralkyl such as the beta-phenyl propyl group, and the part or all of hydrogen atom that connects on the carbon atom in wherein above certain group is by the group of replacements such as halogen atom or cyano group, for example chloromethyl, trifluoro propyl or cyano ethyl.The group of preferred 1-12 carbon atom, the group of 1-8 carbon atom are especially desirable.The a plurality of R bases that exist in the organopolysiloxane can be identical or different.In addition, a is the positive number in the 1.95-2.05.In this organopolysiloxane, molecule chain end is preferably used trimethyl silyl, dimethyl vinyl silicyl, dimethyl hydroxyl silicyl or trivinyl silicyl end-blocking.
This organopolysiloxane preferably contains at least two alkenyls at each molecule, and 0.001-5mol%, the R group of 0.01-0.5mol% alkenyl preferably particularly, even be more preferably vinyl.
Under the situation of combination as the hardening agent of component (C) of using platinum catalyst and organic hydrogen polysiloxanes, the organopolysiloxane that contains alkenyl that often adopts above type is as component (A).
This organopolysiloxane can obtain with common method known to a person of ordinary skill in the art.For example, can under the condition of the molecular structure that produces expectation and the degree of polymerization, carry out the cohydrolysis-condensation (cohydrolysis-condensation) of one or more selected organo-halogen-silanes.As selection, available alkalescence or acidic catalyst carry out the ring-opening polymerization of cyclic polysiloxanes (for example siloxane trimer or tetramer etc.).Although organopolysiloxane is the straight chain diorganopolysiloxaneand basically, it also can comprise part branching.In addition, organopolysiloxane can also be the potpourri with two or more organopolysiloxanes of different molecular structures.
The viscosity of described organopolysiloxane under 25 ℃ is 100mm at least preferably 2/ s.LIMS (liquid injection molding system) viscosity of material is preferably at 100-100,000mm 2In/s the scope.The degree of polymerization preferably is at least 5, more preferably is 10 at least, most preferably at 50-1, in 000 scope.In addition, but the preferred viscosities that is used for rolling stock (millable material) 100,000-10,000,000mm 2In/s the scope, the degree of polymerization preferably is at least 100, and more preferably 3,000 or bigger.The degree of polymerization upper limit is preferably 100,000, even more preferably 10,000.
-(B) the electric conductivity imparting agent-
The electric conductivity imparting agent of component (B) is described below.Type to used electric conductivity imparting agent is not specifically limited.The example of operable material comprises conductive black, and based on particle such as the conductive zinc oxide and the conductive titanate dioxide of conducting metal oxide.The electric conductivity imparting agent can adopt single a kind of material or two or more combinations of different materials.
Can adopt any conductive black commonly used in the conductive rubber composition, example comprises acetylene black, conduction furnace black (CF), superconduction furnace black (super conductive furnace black, SCF), utmost point superconduction furnace black (estra conductive furnace black, XCF), conduction channel black (CC), and the furnace black or the channel black of under about 1500-3000 ℃ high temperature, having heat-treated.The instantiation of commercially available product (representing with its ProductName) comprises acetylene black such as Denka Black (Denki Kagaku Kogyo Co., Ltd. makes) and Shawnigan AcetyleneBlack (Shawnigan Chemical Co., Ltd. makes).The instantiation of conduction furnace black comprises Continex CF (Continental Carbon Co., Ltd. makes) and Vulcan C (CabotCorporation manufacturing).The instantiation of superconduction furnace black comprises ContinexSCF (Continental Carbon Co., Ltd. makes) and Vulcan SC (Cabot Corporation manufacturing).The instantiation of utmost point superconduction furnace black comprises Asahi HS-500 (Asahi CarbonCo., Ltd. makes) and Vulcan XC-72 (Cabot Corporation manufacturing).The instantiation of conduction channel black is Corax L (Degussa AG manufacturing).Other examples comprise carbon black ENSACO260G, ENSACO 250G and ENSACO 210G (Timcal Inc. manufacturing), and they make (being the MMM process) by the oil firing method that does not comprise quick cooling step.In addition, also can adopt Ketjenblack EC-300JD and Ketjenblack EC-600JD (making by KetjenblackInternational Corporation), they all are the furnace black kinds.The quantity of the amount of impurities in these furnace blacks, particularly sulphur and sulphur compound (with the Mass Calculation of element sulphur) preferably is no more than 6000ppm, even 3000ppm or lower more preferably.In above carbon black, acetylene black especially is fit to the present invention, because their impurity content is low, and shows the good secondary structure of development that can bring superior electrical conductivity.In addition, also can adopt the Ketjenblack product valuably, because they have outstanding specific surface area, even a small amount of the interpolation also shows excellent electric conductivity.
The addition of the electric conductivity imparting agent of component (B) should be given the semiconduction level of expectation enough to the curing rubber of conductive silicon rubber composition.Particularly, the amount of component (B) should be enough to guarantee that the specific insulation of cured article is at least 0.1 Ω m, but is no more than 10 14Ω m.Therefore, suitable quantity will depend on the type of used electric conductivity imparting agent, but those of ordinary skills are easy to determine by simple experiment.
Under with the situation of carbon black as the electric conductivity imparting agent, for the organopolysiloxane of per 100 parts of components (A), the amount of carbon black is generally 1-200 part, is preferably 5-50 part.If addition is too big, then carbon black and other components are especially with the physical mixed of component (A) the very difficulty that just becomes.In addition, also can produce other problems, comprise the caoutchouc elasticity that the cured article physical strength reduces and can not obtain to expect.
Under the situation of particle as the electric conductivity imparting agent of using based on conducting metal oxide, because this particle has high specific gravity, for per 100 parts of components (A), described particle addition is preferably 30-200 part, even 50-200 part more preferably.
-(C) hardening agent-
The hardening agent of component (C) can adopt the combination of platinum based catalyst and organic hydrogen polysiloxanes (organohydrogenpolysiloxane) (a kind of addition-crosslinked hardening agent), perhaps can adopt organic peroxide catalyst (a kind of radical crosslinking hardening agent).Hardening agent is to be enough to realizing that the amount that rubber composition effectively solidifies adds.
The combination of platinum based catalyst and organic hydrogen polysiloxanes is the known hardening agent of the silicon-ketone composition of conventional addition-curable, and when adopting this hardening agent, general each molecule of the organopolysiloxane of component (A) contains at least two kiki alkenyl groups as mentioned above.
The molecular structure of organic hydrogen polysiloxanes can be straight chain, side chain or ring texture, but the degree of polymerization preferably is no more than 300.The example of organic hydrogen polysiloxanes comprises terminal diorganopolysiloxaneand (diorganopolysiloxanes) with dimethyl hydrogen silicyl end-blocking; The multipolymer that comprises dimethyl siloxane units, methyl hydrogen siloxane unit and terminal trimethylsiloxy unit; Comprise dimethyl hydrogen siloxane unit (H (CH 3) 2SiO 0.5The unit) and SiO 2The low viscosity fluid of unit; 1,3,5,7-tetrahydrochysene-1,3,5,7-tetramethyl-ring tetrasiloxane, 1-propyl group-3,5,7-three hydrogen-1,3,5, the 7-tetramethyl-ring tetrasiloxane, and 1,5-dihydro-3,7-dihexyl-1,3,5,7-tetramethyl-ring tetrasiloxane.
The addition of organic hydrogen polysiloxanes preferably be enough to make direct-connected hydrogen atom on the silicon atom with respect to the ratio of the kiki alkenyl group in the organopolysiloxane of component (A) in the 50-500mol% scope.
Any conventional platinum based catalyst all can be used as the platinum based catalyst with the organic hydrogen polysiloxanes combination.Example comprises simple elements platinum, platinum complex, platinum compounds such as chloroplatinic acid, and the complex of chloroplatinic acid and alcoholic compound, aldehyde compound, ether compound and various alkene.The addition of platinum based catalyst (with respect to the organopolysiloxane quality of component (A) Mass Calculation with pt atom) is preferably 1-2000ppm.
On the other hand, the example of organic peroxide that can be used as the hardening agent of component (C) comprises alkyl peroxide, as di-t-butyl peroxide, 2, and 5-dimethyl-2,5-two (t-butylperoxy) hexane and dicumyl peroxide.The addition of organic peroxide is 0.1-10 part with respect to per 100 parts of components (A) organopolysiloxane preferably.
The hardening agent of component (C) also can adopt the combination of above-mentioned addition-crosslinked hardening agent and organic peroxide, makes addition-crosslinked and free radical reaction is crosslinked all is initiated.At rubber composition is under the situation of fluent material, recommends to adopt the hardening agent of addition-crosslinked hardening agent as component (C).
-other components-
Following other components also can add in the rubber composition of the present invention as required, and condition is that the adding of these other components can not damage purpose of the present invention or effect.
-enhancing fine silicon dioxide powder:
Need to strengthen the curing rubber that the fine silicon dioxide powder obtains the physical strength excellence, the specific surface area of SiO 2 powder preferably is at least 10m 2/ g most preferably is 50-400m 2/ g.The example of this fine silicon dioxide powder comprises pyrogenic silica (dry method silicon dioxide) and precipitated silica (wet method silicon dioxide), preferred pyrogenic silica (dry method silicon dioxide).In addition, the surperficial available organopolysiloxane of these fine silicon dioxide powder, organic polysilazane, chlorosilane or alkoxy silane etc. carry out hydrophobic treatments.The suitable instantiation that strengthens silicon dioxide powder that is purchased comprises Aerosil 130,200,300 and 380 (trade names, Nippon Aerosil Co., Ltd. manufacturing), Cab-O-sil MS-5, MS-7, HS-5 and HS-7 (trade name, the CabotCorporation manufacturing), Santocel FRC and CS (trade name, Monsanto Company Ltd. makes), and Nipsil VN-3 (Ltd. makes for trade name, Nippon Silica Industry Co.).These silica products can use separately, or two or more different products are used in combination.Though the addition to the fine silicon dioxide powder is not specifically limited, if consider to strengthen effect and to the influence of the processability and the electric conductivity of resulting composition, the quantity of silicon dioxide powder is preferably 1-50 part, for 100 parts of organopolysiloxanes.
-other adjuvants
Addible other adjuvants comprise colorant, such as the heat-resisting improver of iron octoate, such as the fire retardant of halogen compounds, store up sour agent (acid receiver), iron oxide and ceria, thermal conductivity improver, release agent, and the filler (for example crystalline silica of Fen Suiing and kieselguhr micropowder) that plays replenishers (extender) effect.In addition, other possible adjuvants comprise spreading agent, as alkoxy silane, dimethicone oils and silanol (comprising that two ends are all with the silanol low-molecular-weight siloxane of diphenyl silanodiol end-blocking for example) with degree of polymerization lower than the organopolysiloxane of component (A), and improve the carbon functional silane of the adhesiveness of composition and molding performance and do not damage the crosslinked curing of silicone component of composition or uncured alkylene elastomer.
-preparation-
Rubber composition of the present invention can obtain by using such as the even mixing said ingredients of the mixing arrangement of two roller kneaders, Banbury mixer, puy (kneading machine), Shinagawa mixer or planet mixer.
[preparation method of silicone member]
-once crosslinked
In preparation method of the present invention, with the rubber composition of aforesaid way preparation molding on base material earlier, can be with or without the middle layer between its they, solidify the cured article that described composition forms molding then.
Molding and curing are not specifically limited, can adopt conventional method.Also can adopt the foamed solidification method.Heating and curing are not specifically limited, can adopt any conventional method, condition provides enough heats with the silicone component in the cross-linked composition.Molding methods also is not specifically limited, and possible method comprises the continuous vulcanization of adopting the extrusion molding method, and the mould molding that adopts compression moulding or injection moulding.A this cross-linking process be molded into 70-500 ℃, carry out under preferred 120-300 ℃ the heating-up temperature, be several seconds to 1 hour heat time heating time, preferred 10 seconds-30 minutes.Heating preferably should be carried out under alap temperature, and heat time heating time should be short as far as possible.
In to this method more detailed description, rubber composition with stratiform form (being sheet or film) molding, can be with or without the middle layer at the base material top between them, then heating and hardening composition.The example in middle layer comprises prime coat or caoutchouc elasticity adhesive phase, and this middle layer is applied on the base material in advance.Making electrostatic printing apparatus with under the situation of roller, base material is plug, metal tape or resin strip etc., and is making under the situation of electrostatic printing apparatus with band, and base material is the base material of belt shape.One-step solidification forms the stratiform silicone member on base material.
-secondary cross-linking
The cured article of the molding of Huo Deing be not higher than 5.0 * 10 subsequently in the above described manner 4Handle under the pressure of Pa and the 80-180 ℃ temperature.
The cured article that the condition of special recommendation relates to described molding be not higher than 5.0 * 10 4Pa (380 holder) preferably is not higher than 1.0 * 10 4The pressure of the reduction of Pa (76 holder) and 80-180 ℃ are heat-treated under preferred 80-150 ℃ the temperature.Especially it is desirable to be not higher than 2.0 * 10 3The pressure of the reduction of Pa (15 holder) carries out this decompression thermal treatment down and under 80-180 ℃ the temperature.This decompression heat treatment period can suitably be set according to pressure and temperature, but generally is not shorter than 10 minutes, preferred 60 minutes or longer.
It is many more that pressure reduces, and the quantity of removable volatile constituent such as low-molecular-weight siloxane is just big more, and just can prevent better that silicone is by the oxygen oxidation.Therefore, low pressure limit is not specifically limited, but proceeds from the reality, lower limit is generally about 1.0 * 10 2Pa-1.0 * 10 3In the Pa scope.In addition, lower treatment temperature reduces the degraded of silicone polymer, but has also reduced the clearance of above-mentioned volatile low-molecular-weight siloxane component, and therefore this processing is carried out under at least 80 ℃ temperature.
Be not specifically limited being used to carry out above decompression heat-treating methods, adoptable device example comprises the thermal treatment exsiccator of vacuum drying apparatus, vacuum dryer or the employing radiation heating etc. that are purchased.An instantiation is vacuum dehydrating at lower temperature device DRV420DA (trade name, AdvantecGroup makes).
The silicone member of molding is a semiconduction in the above described manner.In other words, specific insulation is at 0.1 Ω m-10 14In the Ω m scope, make this member can be used as the roller of electrostatic printing apparatus or the structural elements of band.
If desired, can further apply another layer at the semiconduction silastic-layer that plays the silicone member effect that forms on the base material (can be provided with or not be provided with the middle layer between silastic-layer and the base material), as polyurethane-base coating or silicone-based coating.These extra layers can be used for such as protection, prevent the low-molecular-weight siloxane component ooze out, anti-scratch, improve smooth property, give the purpose of wearing quality, or be used for some other purpose.
[embodiment]
With a series of embodiment and comparative example the present invention is described in further detail below, but the embodiment that the present invention is subjected to hereinafter proposing never in any form limits.In following examples and comparative example, " part " refers to " mass parts ", and viscosity number refers to use the value of Brookfield rotary viscosity measuring under 25 ℃.
[embodiment 1]
With kneading machine following material is mixed:
-100 parts of organopolysiloxanes, viscosity 1 * 10 7Mm 2/ s comprises 99.825mol% dimethyl siloxane units and 0.15mol% methyl vinyl siloxane unit, and two molecule chain ends are all by the dimethyl vinyl silicyl end-blocking of 0.025mol%,
-10 parts of pyrogenic silicas, specific surface area 200m 2/ g (Nippon Aerosil Co., Ltd. make) and
-2 parts of dimethylpolysiloxanepolymer polymer, the silanol end-blocking is all used at two ends, degree of polymerization 3-10, as spreading agent,
In this potpourri of 160 ℃ of following thermal treatments 2 hours, obtain base compound A then.
Then with twin-roll plastic mixing mill with 12 parts play the effect of electric conductivity imparting agent be called DenkaBlack (particle mean size: 40nm, trade name, Denki Kagaku Kogyo Co., Ltd. makes) acetylene black add and be distributed among 100 parts of base compound A, obtain conductive rubber mixing material A.
Use twin-roll plastic mixing mill, with 100 parts of this conductive rubber mixing material A, with the methylhydrogenpolysi,oxane (degree of polymerization: 17 that on strand two ends and non-terminal position in strand, contains the hydrogen atom that silicon atom is connected as 2.1 parts of crosslinking chemical, the quantity of the hydrogen atom that silicon atom connects: 0.0060mol/g), as 0.1 part of ethynylcyclohexanol and 0.1 part of platinum catalyst (Pt concentration: 1%) mix, obtain curable silicone rubber composition of reaction suppressor.
Around the plug of diameter 6mm, form the coating of thick 6mm with the composition of such acquisition, with the resulting structures molding and be solidified into the roll shape of overall diameter 18mm, long 50mm.In addition, also with the said composition sample molded and be solidified into the sheet of thickness 2mm.Used molding and condition of cure relate to elder generation and carried out pressure-cure (press curing) 15 minutes under 120 ℃, pass through 1.0 * 10 then 3Carrying out secondary cross-linking in 4 hours 150 ℃ of heating under the decompression of Pa (7.5 holder) handles.
To handle the roller (being called silica gel roller) that is included in the surperficial cure silicone rubber layer that forms that obtains through above curing and be cut into the 16mm diameter with muller, then with the roller surface grinding to the surfaceness that is not more than 10 μ m, thereby form roller with smooth surface.With the performance of being infected with of following method evaluation gained silica gel roller, and the pressure after being compressed falls into degree (degree ofindentation).
Be infected with performance
Estimate the performance of being infected with of silica gel roller with the following methods, promptly the OPC drum that is caused by the silicone component of the cure silicone rubber layer that oozes out roller is infected with.
(LaserPress 4150PS) takes off toner cartridge (tonercartridge) from the Canon laser printer, by applying 1kg weight respectively at the roller two ends, the silastic-layer surface pressure of silica gel roller roused on the surface at OPC.Kept this state 24 hours.Then toner cartridge is reinstalled on the printer, on printer paper, carries out full paper ash degree and print.If above pressing operation has caused the silicone component to ooze out silica gel roller and move on the OPC drum, then will be reflected on the printer paper as stain by the impression that is pressed in the zone on the OPC drum at the silicone roller.Print continuously, measure the printer paper quantity of having printed when naked eyes no longer can be seen the impression stain on the printer paper.
-press and fall into (indentation)
Take off the silica gel roller that is pressed in a manner described on the OPC drum, after the compression that roller produces from above pressing operation discharges 1 hour, measure owing to fall into degree (promptly pressing the sunken degree of depth) by being pressed in the pressure that the silica gel roller that causes on the OPC drum still keeps.It is very important performance that the sunken degree of this pressure is used as under the situation of developer roll at silica gel roller.If the toner layer that toner obtains in attached in press falling into, then pressing and falling into will be thicker than the peripheral region, mean that toner layer thickness becomes irregular, cause the printing density fluctuation.Therefore, littler above pressure falls into the better developer roll of value generation.
In addition, the thick silicone rubber plate of the 2mm that employing prepares is above estimated physical property and low-molecular-weight siloxane content with the following methods.
-physical property
Measure hardness (A type hardness tester meter) and the compression set under 180 ℃/22 hours according to JIS K 6249.Measure rebound resilience according to JIS K 6255.
-low-molecular-weight siloxane content
The small pieces silicone rubber plate of heavy 1g immersed in the acetone soln that contains the 20ppm n-tetradecane and to extract in 8 hours.Make temperature be elevated to 270 ℃ from 50 ℃ with 10 ℃/minute programming rates, measure the gained sample by FID intensification vapor-phase chromatography.Used post is J﹠amp; The DB1701 post that W Scientific Inc. makes, carrier gas is He.By with respect to peak area as the n-tetradecane of standard, measure the peak surface area, calculate the concentration of low-molecular-weight siloxane.
That more than estimates the results are shown in the table 1.
[embodiment 2]
Prepare sheet material and roller with embodiment 1 same way as, but change the condition of secondary cross-linking, with the pressure of the reduction of secondary cross-linking from 1.0 * 10 3Pa (7.5 holder) becomes 1.0 * 10 4Pa (76 holder).
[embodiment 3]
Prepare sheet material and roller with embodiment 1 same way as, but change the condition of secondary cross-linking, with the pressure of the reduction of secondary cross-linking from 1.0 * 10 3Pa (7.5 holder) becomes 5.0 * 10 4Pa (380 holder).
[embodiment 4]
Prepare sheet material and roller with embodiment 1 same way as, but change the condition of secondary cross-linking, the temperature of secondary cross-linking is become 80 ℃ from 150 ℃.
[comparative example 1]
Prepare sheet material and roller with embodiment 1 same way as, but do not carry out embodiment 1 described secondary cross-linking.
[comparative example 2]
Prepare sheet material and roller with embodiment 1 same way as, but change the secondary cross-linking condition that embodiment 1 describes, the thermal treatment of will reduce pressure becomes heating under normal pressure under 230 ℃ heat-treated in 4 hours.
[comparative example 3]
Prepare sheet material and roller with embodiment 1 same way as, but change the secondary cross-linking condition that embodiment 1 describes, the thermal treatment of will reduce pressure becomes heating under normal pressure under 200 ℃ heat-treated in 4 hours.
[comparative example 4]
Prepare sheet material and roller with embodiment 1 same way as, but change the secondary cross-linking condition that embodiment 1 describes, the thermal treatment of will reduce pressure becomes heating under normal pressure under 180 ℃ heat-treated in 4 hours.
[comparative example 5]
Prepare sheet material and roller with embodiment 1 same way as, but change the secondary cross-linking condition that embodiment 1 describes, the thermal treatment of will reduce pressure becomes heating under normal pressure under 200 ℃ heat-treated in 24 hours.
[comparative example 6]
Prepare sheet material and roller with embodiment 1 same way as, but change the secondary cross-linking condition that embodiment 1 describes, the thermal treatment of will reduce pressure becomes heating under normal pressure under 150 ℃ heat-treated in 24 hours.
Estimate silica gel roller and the silicon rubber sheet material that obtains in embodiment 2 to 4 and the comparative example 1 to 6 in embodiment 1 identical mode.The results are shown in table 1 and the table 2.
[table 1]
Figure A20081000197300161
[table 1 note]
(1) value of material hardness, rebound resilience, compression set and low-molecular-weight siloxane content all refers to the data measured behind the secondary cross-linking.
(2) Dn: contain n [(CH 3) 2SiO] annular siloxane of unit.
[table 2]
Figure A20081000197300171
[table 2 note]
(1) except that comparative example 1, the value of material hardness, rebound resilience, compression set and low-molecular-weight siloxane content all refers to the data measured behind the secondary cross-linking.
(2) Dn: contain n [(CH 3) 2SiO] annular siloxane of unit.
From table 1 and 2 as seen, carry out secondary cross-linking under the decompression heating condition that in preparation method of the present invention, defines and in the roller for preparing, the amount of low-molecular-weight siloxane can effectively be reduced.In addition, be clear that equally, move to OPC drum that OPC drum causes by silicone components from roller and be infected with (representing) and also can be reduced, and press the degree of falling into also advantageously to be reduced by being infected with number of copies.
Industrial applicability
Electrostatic printing apparatus with preparation method's preparation of the present invention can with the semiconductor silicon rubber component Be particularly useful as the rubber component that directly or indirectly contacts with OPC drum or toner, for example can be used as quiet The various rollers that adopt in the electricity printing equipment and the structural material of band. Specifically, described rubber structure Part can be used as developer roll, strip-like developing pipe, toner conveying sponge roller, transfer roller, conveyer belt, photographic fixing The structural material of roller and fixing band etc.

Claims (9)

1. electrostatic printing apparatus is with the preparation method of semiconductor silicon rubber component, and this method may further comprise the steps:
The rubber composition layer that comprises following component by molding on base material solidifies the cured article that said composition forms molding then:
(A) 100 mass parts are by the following average organopolysiloxane of forming general formula (1) expression:
R nSiO (4-n)/2 (1)
(wherein the R representative replaces or unsubstituted monovalence alkyl, and n represents the number of 1.95-2.05),
(B) the electric conductivity imparting agent of q.s, with give semiconduction and
(C) hardening agent of q.s is with can curing component (A),
Wherein can be provided with or not be provided with the middle layer between base material and the rubber composition layer; With
Be no more than 5.0 * 10 comprising 4The cured article of this molding of thermal treatment under the condition of the pressure of Pa and 80-180 ℃ temperature.
2. the process of claim 1 wherein that described base material is the plug of electrostatic printing apparatus with roller, or the electrostatic printing apparatus band shape base material of band.
3. the method for claim 1, wherein said base material is the plug of electrostatic printing apparatus with roller, described rubber composition molding and be cured as layer on the mandrel outer perimeter surface, wherein be provided with or be not provided with the middle layer between base material and the rubber composition layer, thereby form the silastic-layer that solidifies, then the silastic-layer that thermal treatment should be solidified under the pressure that reduces under the described conditions.
4. claim 2 or 3 method, wherein said electrostatic printing apparatus roller is that developer roll, toner are carried sponge roller, cleaning sponge roller or fixing roller.
5. the method for claim 1, wherein said base material is the band shape base material of electrostatic printing apparatus with band, described rubber composition is at this band shape base material top molding and be cured as layer, wherein between base material and rubber composition layer, be provided with or be not provided with the middle layer, thereby form the silastic-layer of at least one curing, the silastic-layer that solidifies is somebody's turn to do in thermal treatment under the described conditions then.
6. claim 2 or 5 method, wherein said electrostatic printing apparatus is strip-like developing pipe or photographic fixing band with band.
7. the electrostatic printing apparatus semiconductor silicon rubber component of the method for claim 1 preparation.
8. electrostatic printing apparatus roller comprises the semiconductor silicon rubber component of claim 7.
9. electrostatic printing apparatus comprises the semiconductor silicon rubber component of claim 7 with being with.
CNA2008100019731A 2007-01-05 2008-01-04 Method for preparing semiconductive silicone rubber components for electrophotographic apparatus, and roll and belt for electrophotographic apparatus having the silicone rubber components Pending CN101276167A (en)

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