JP4840560B2 - Conductive roller and method for improving adhesion between silicone rubber elastic layer and surface layer thereof - Google Patents

Description

The present invention relates to a conductive roller having a volume resistivity of 10 kΩ · m or less provided with a conductive metal core, a silicone rubber elastic layer provided around the metal core, and a surface layer made of resin around the metal core. The present invention relates to a conductive roller excellent in durability as a roller, in particular, adhesion durability with a resin layer as a surface layer, and a method for improving adhesion between a silicone rubber elastic layer and a surface layer in the conductive roller .

Conventionally, a conductive roller in which a conductive elastic layer is coated around a metal core has been widely used for copying machines and printers. Particularly elastic layer, electrically insulating conductive rubber blended with conductive material in a rubber-like substance exhibiting are various known, blended and carbon black, for example, as a conductive material, an electrical resistivity of 10 ^-3 to Conductive rubber having a range of 10 ⁻¹ Ω · m is applied in a wide range of fields.

  On the other hand, silicone rubber, which is one of the electrically insulating rubbery substances, is excellent in heat resistance, cold resistance and weather resistance, and is widely used as an electrically insulating rubber, but it is conductive like other rubbery substances. It is also put into practical use as a conductive rubber by adding materials.

  In this case, examples of the conductive material added to the conductive silicone rubber composition include various metal powders such as carbon black, graphite, silver, nickel, and copper, various non-conductive powders, and short fiber surfaces with a metal such as silver. What is treated with, mixed with carbon fiber, metal fiber, etc., without impairing the unique properties of rubber, the electrical resistivity of silicone rubber up to 10kΩ · m or less depending on the type and filling amount of the conductive material It is frequently used because it can be lowered.

  In particular, a liquid addition-curing type silicone rubber composition is widely used as a roll material because it is excellent in moldability and can be cured in a short time. However, silicone rubber contains a trace amount of oligomer components that do not participate in crosslinking, which contaminates the photoreceptor or aggregates the toner, and therefore requires a resin layer as a surface layer. However, since silicone rubber is excellent in releasability, it is difficult to bond a resin to the cured rubber. In addition, the liquid addition curable silicone rubber composition is excellent in moldability, but if the viscosity is too low, leakage from the molding machine may occur, or if it is too high, variation in electrical resistance in the roll will increase. Problem arises. Furthermore, when the strength as a cured silicone rubber is insufficient, the durability is inferior when the roll is incorporated into an electrophotographic apparatus as a roll, and rubber breakage occurs. In order to improve this, when fumed silica or precipitated silica is added, not only the compression set is deteriorated, but also a great problem occurs that the resistance changes with time.

  As a countermeasure against such a problem, Japanese Patent Application Laid-Open No. 2005-82617 (Patent Document 1) discloses a stable volume resistivity with a small compression set by blending an inorganic filler having a specific particle diameter and bulk density. However, there is no description on the adhesion to the surface layer, and no mention is made of the curability of the rubber composition, which is an important point. In JP-A-2003-321610 (Patent Document 2), it is disclosed that a conductive rubber having low hardness and low compression set can be obtained by adding carbon black to a specific silicone polymer. There is no specific description about the surface layer, and therefore no suggestion has been made about the adhesion to the surface layer. Japanese Patent Application Laid-Open No. 2004-37665 (Patent Document 3) describes the curability of liquid rubber at 100 ° C., which is described for obtaining stable resistance. There is no mention of adhesiveness. Furthermore, at 100 ° C., the actual curing temperature is too low.

JP 2005-82617 A JP 2003-321610 A JP 2004-37665 A

The present invention has been made in view of the above circumstances, and is an electrophotographic image of a conductive roller, particularly a copying machine or a printer, which has excellent adhesion to a surface layer resin, low compression set, and excellent durability. To provide a conductive roller suitably used as a charging roller, a developing roller, a toner conveying roller, a transfer roller, and a cleaning roller in a forming apparatus, and a method for improving the adhesion between a silicone rubber elastic layer and a surface layer in the conductive roller. With the goal.

As a result of intensive studies to achieve the above object, the present inventor has found that a conductive metal core, a silicone rubber elastic layer provided around the metal core, and a conductive layer provided with a resin surface around the metal core. When the 10% curing time at 120 ° C. is T10 (seconds) and the 90% curing time is T90 (seconds), the above-mentioned silicone rubber elastic layer is 30 seconds ≦ T10 ≦ 120 seconds and 20 seconds. ≦ T90−T10 ≦ 120 seconds when cured curable silicone rubber composition is used, it is excellent in adhesion to the resin layer of the surface layer, and has a small compression set and excellent durability. As a result, the present invention has been made.
Accordingly, the present invention provides the following conductive roller and a method for improving the adhesion between the silicone rubber elastic layer and the surface layer of the conductive roller.
Claim 1:
A conductive roller having a conductive metal core, a silicone rubber elastic layer provided around the metal core, and a surface layer made of resin around the metal core, wherein the silicone rubber elastic layer comprises:
(A) The alkenyl group content containing an alkenyl group bonded to at least two silicon atoms in one molecule is 1.0 × 10 ⁻⁶ mol / g to 5.0 × 10 ⁻³ mol / g, It is an organopolysiloxane which is liquid at room temperature (25 ° C.) having a polystyrene-equivalent weight average degree of polymerization of 100 to 1,000 in gel permeation chromatography analysis , and 0.5 to 20% by mass of the organopolysiloxane is containing vinyl group bonded to 4-50 silicon atoms in a molecule, Ru vinyl group content of ^{3.0 × 10 -4 mol / g~1.4 ×} 10 -2 mol / g der polymerization 100 parts by mass of an organopolysiloxane having a degree of 4 to 600,
(B) containing hydrogen atoms bonded to at least two silicon atoms (Si-H groups) in a molecule, Si-H group content of Ru 0.001~0.017mol / g Der organohydrogen 0.1 to 30 parts by mass of polysiloxane,
(However, the Si-H group in the component (B) relative to the alkenyl group in the component (A)
Of the molar ratio of 0.3 to 5.0)
(C) 0.5-50 parts by mass of an inorganic filler,
(D) Conductivity-imparting material selected from conductive carbon black having a specific surface area of 30 to 120 m ² / g, iodine adsorption of 30 to 120 mg / g, and DBP oil absorption of 100 to 200 ml / 100 g Volume resistance of cured product In an amount of 10 kΩ · m or less,
(E) addition reaction catalyst catalyst amount,
(F) When the 10% curing time at 120 ° C. of the composition is T10 (seconds) and the 90% curing time is T90 (seconds), T10 and T90 are 30 seconds ≦ T10 ≦ 120 seconds and 20 seconds ≦ T90, respectively. -T10 as an essential component an addition reaction control agent in an amount to ≦ 120 seconds state, and are not viscosity curing the curable silicone rubber composition of 10-100 Pa · s at 25 ° C., the silicone rubber composition was 5 minutes press cured at 0.99 ° C., the volume resistivity when the 4 hours post-cured at 200 ° C. is the 0.1Ω · m~10kΩ · m, 20-60 der Rukoto hardness by durometer type a Characteristic conductive roller.
Claim 2 :
(F) the amount of component is an amount to T10 of 58 seconds ≦ T10 ≦ 70 seconds at 120 ° C. of the composition according to claim 1 conductive roller according.
Claim 3 :
The conductive roller according to claim 1 or 2 , wherein the blending amount of the component (F) is such that T90 at 120 ° C of the composition is 30 seconds ≤ T90-T10 ≤ 90 seconds.
Claim 4 :
Conductive carbon black, conductive roller of any one of claims 1 to 3, wherein the acetylene black.
Claim 5 :
Conductive roller of any one of claims 1-4, wherein the tensile strength of the silicone rubber layer is not less than 2.0 MPa.
Claim 6 :
The conductive roller according to any one of claims 1 to 5 , wherein the compression set of the silicone rubber layer at 180 ° C for 22 hours (25%) is 10% or less.
Claim 7 :
The conductive roller according to any one of claims 1 to 6 , wherein the resin forming the surface layer is a resin containing a urethane bond and / or an amide bond.
Claim 8 :
Conductive roller, developing roller, charging roller and the conductive roller of any one of claims 1 to 7 are those selected from the transfer roll.
Claim 9 :
Method for improving the adhesion between the silicone rubber elastic layer and the surface layer in a conductive roller having a conductive metal core, a silicone rubber elastic layer provided around the metal core, and a surface layer made of resin around the metal core A silicone rubber composition layer according to any one of claims 1 to 4 is formed on the core metal and cured at a temperature of 120 to 300 ° C for 1 minute to 3 hours. A method for improving adhesion between the silicone rubber elastic layer and the surface layer, wherein a rubber elastic layer is formed and a surface layer made of a resin is formed around the rubber elastic layer.
Claim 10 :
The method according to claim 9 , wherein the silicone rubber composition is molded by any one of injection molding, injection molding, and coating.
Claim 11 :
Furthermore, the method of Claim 9 or 10 which performs the postcure for 30 minutes-70 hours at 120-250 degreeC.
Claim 12 :
The method according to any one of claims 9 to 11 , wherein the resin forming the surface layer is a resin containing a urethane bond and / or an amide bond.

  The conductive roller of the present invention is excellent in durability for adhesion to the surface layer resin and has a small compression set.

  The conductive roller of the present invention is a conductive roller provided with a conductive metal core, a silicone rubber elastic layer provided around the metal core, and a surface layer made of resin around the metal core. When the layer has a 10% curing time at 120 ° C. of T10 (seconds) and a 90% curing time of T90 (seconds), 30 seconds ≦ T10 ≦ 120 seconds and 20 seconds ≦ T90−T10 ≦ 120 seconds. A curable silicone rubber composition is cured.

  In this case, the curable silicone rubber composition is an addition-curable silicone rubber composition, particularly a liquid addition-curable silicone rubber composition having a viscosity of 10 to 100 Pa · s at 25 ° C. A cured product of the silicone rubber composition is preferred. In the present invention, the viscosity is a value measured with a rotational viscometer.

As such a silicone rubber layer,
(A) 100 parts by mass of an organopolysiloxane containing an alkenyl group bonded to at least two silicon atoms in one molecule;
(B) 0.1-30 parts by mass of an organohydrogenpolysiloxane containing hydrogen atoms bonded to at least two silicon atoms in one molecule;
(C) 0.5-50 parts by mass of an inorganic filler,
(D) Conductivity-imparting material An amount that makes the volume resistance of the cured product 10 kΩ · m or less,
(E) Addition reaction catalyst It is preferable that the silicone rubber composition having a catalytic amount as an essential component is cured.

  Here, the organopolysiloxane containing an alkenyl group bonded to at least two silicon atoms in one molecule of component (A) is the main component (base polymer) of the present composition, and this alkenyl group-containing organopolysiloxane. As for, what is shown by the following average compositional formula (1) can be used.

R ¹ _a SiO _{(4-a) / 2} (1)
In the above formula (1), R ¹ is an unsubstituted or substituted monovalent hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, which are the same or different from each other, and a is 1.5 to 2.8, The positive number is preferably 1.8 to 2.5, more preferably 1.95 to 2.02. Here, as the unsubstituted or substituted monovalent hydrocarbon group bonded to the silicon atom represented by R ¹ , a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, Pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group, alkyl group such as decyl group, aryl group such as phenyl group, tolyl group, xylyl group, naphthyl group, benzyl group, phenylethyl group, phenylpropyl An aralkyl group such as a group, a vinyl group, an allyl group, a propenyl group, an isopropenyl group, a butenyl group, a hexenyl group, a cyclohexenyl group, an alkenyl group such as an octenyl group, etc., or a part or all of the hydrogen atoms of these groups Substituted by halogen atoms such as fluorine, bromine and chlorine, cyano groups, etc., such as chloromethyl group, chloro Propyl group, bromoethyl group, trifluoropropyl group, but cyanoethyl group and the like, 90 mol% or more of all R ¹ groups, except for alkenyl groups (90 to 100 mole%), particularly 95 mol% or more (95 to 100 Mol%) is preferably a methyl group. In addition, at least two of R ¹ (usually 2 to 50, particularly 2 to 30) are alkenyl groups (preferably those having 2 to 8 carbon atoms, more preferably 2 to 6 and particularly preferably vinyl. Group).

In the above formula (1), the alkenyl group content in the organopolysiloxane is 1.0 × 10 ⁻⁶ mol / g to 5.0 × 10 ⁻³ mol / g, particularly 5.0 × 10 ^−6. It is preferable to set it as mol / g-1.0 * 10 < ^-3 > mol / g. If the amount of the alkenyl group is less than 1.0 × 10 ⁻⁶ mol / g, crosslinking may be insufficient and gelation may occur, and if it exceeds 5.0 × 10 ⁻³ mol / g, compression set Not only may worsen, but also may become brittle rubber. This alkenyl group may be bonded to a silicon atom at the end of the molecular chain, may be bonded to a silicon atom in the middle of the molecular chain, or may be bonded to both.

  The structure of this organopolysiloxane is basically a linear structure in which the main chain is composed of repeating diorganosiloxane units and both ends of the molecular chain are blocked with triorganosiloxy groups. May have a branched structure, a ring structure, or the like. The degree of polymerization may be liquid at room temperature (25 ° C.) (for example, the viscosity at 25 ° C. is about 100 to 1,000,000 mPa · s, preferably about 200 to 100,000 mPa · s). The degree (for example, the weight-average polymerization degree in terms of polystyrene in GPC (gel permeation chromatography) analysis, etc., the same shall apply hereinafter) is preferably 100 to 1,000, particularly preferably 100 to 800, and more preferably 150 to 600. is there. If it is less than 100, rubber elasticity may be insufficient, and if it exceeds 1,000 (for example, so-called raw rubber-like organopolysiloxane), compression set may be deteriorated.

  In the present invention, among the organopolysiloxane of component (A) having at least two alkenyl groups, 0.3 to 20% by mass, preferably 0.5 to 15% by mass is at least 4 in one molecule. (Normally 4 to 50), preferably 5 or more (for example, 5 to 30) organopolysiloxane having a vinyl group bonded to silicon atoms.

  As such an organopolysiloxane, those represented by the following average composition formula (2) can be used.

R ² _b SiO _{(4-b) / 2} (2)
In the formula (2), R ² is 1 to 10 carbon atoms the same or different from each other, preferably unsubstituted or substituted monovalent hydrocarbon group of 1 to 8, a is 1.5 to 2.8, The positive number is preferably 1.8 to 2.5, more preferably 1.95 to 2.02. Here, the unsubstituted or substituted monovalent hydrocarbon group bonded to the silicon atom represented by R ² excluding the vinyl group includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert group, -Alkyl groups such as butyl group, pentyl group, neopentyl group, hexyl group, cyclohexyl group, octyl group, nonyl group, decyl group, aryl group such as phenyl group, tolyl group, xylyl group, naphthyl group, benzyl group, phenylethyl Groups, aralkyl groups such as phenylpropyl groups, etc., in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms such as fluorine, bromine, chlorine, cyano groups, etc., such as chloromethyl group, chloropropyl group, bromoethyl Group, trifluoropropyl group, cyanoethyl group, etc., but 90 mol% of all R ² groups excluding vinyl group The above (90 to 100 mol%), particularly 95 mol% or more (95 to 100 mol%) is preferably a methyl group. Further, at least 4 (usually 4 to 50), preferably 5 or more (for example, 5 to 30) of R ² are required to be vinyl groups. If it is less than 4, sufficient adhesion to the surface layer may not be obtained.

In the above formula (2), the vinyl group content in the organopolysiloxane is 3.0 × 10 ⁻⁴ mol / g to 1.4 × 10 ⁻² mol / g, particularly 5.0 × 10 ^−4. It is preferable to set it as mol / g-5.0 * 10 < ^-3 > mol / g. If the amount of the vinyl group is less than 3.0 × 10 ⁻⁴ mol / g, adhesion to the surface layer may be insufficient. The vinyl group may be bonded to a silicon atom at the end of the molecular chain and a silicon atom in the middle of the molecular chain, or may be bonded only to a silicon atom in the middle of the molecular chain.

  The structure of this organopolysiloxane is basically a linear structure in which the main chain is composed of repeating diorganosiloxane units and both ends of the molecular chain are blocked with triorganosiloxy groups. May be a branched structure or a ring structure. The degree of polymerization is 4 to 600, preferably 10 to 500, and more preferably 20 to 300. If it is less than 4, it is difficult to have 4 or more vinyl groups, and if it is 600 or more, the effect on adhesiveness is reduced.

The component (B) is an organohydrogenpolysiloxane having at least 2, preferably 3 or more hydrogen atoms (Si-H groups) bonded to silicon atoms in one molecule, and the Si-H groups in the molecule are The alkenyl group bonded to the silicon atom in the component (A) is crosslinked by a hydrosilyl addition reaction, and acts as a curing agent (crosslinking agent) for curing the composition. The organohydrogenpolysiloxane of the component (B) is represented by the following average composition formula (3), and is at least 2 (usually 2 to 300), preferably 3 or more (for example, 3 to 3) in one molecule. 200), more preferably those having 3 to 100 silicon-bonded hydrogen atoms are preferably used.
R ³ _c H _d SiO _{(4-cd) / 2} (3)
(Wherein R ³ is a substituted or unsubstituted monovalent hydrocarbon group having 1 to 10 carbon atoms, c is 0.7 to 2.1, d is 0.001 to 1.0, and c + d is a positive number satisfying 0.8 to 3.0.)

Here, examples of the monovalent hydrocarbon group for R ³ include the same groups as those exemplified for R ¹ , but those having no aliphatic unsaturated group are preferred. Further, c is preferably a positive number satisfying 0.8 to 2.0, d is preferably 0.01 to 1.0, and c + d is preferably 1.0 to 2.5. The molecular structure of siloxane may be any of linear, cyclic, branched, and three-dimensional network structures. In this case, the number of silicon atoms in one molecule (or the degree of polymerization) is preferably 2 to 300, particularly about 4 to 150 at room temperature (25 ° C.).

  The silicon atom-bonded hydrogen atom (Si—H group) content is preferably 0.001 to 0.017 mol / g, particularly 0.002 to 0.015 mol / g in the organohydrogenpolysiloxane. If the amount of silicon atom-bonded hydrogen atoms (Si—H groups) is too small, crosslinking may be insufficient and gelation may occur, and if too large, the crosslinking density becomes too high, resulting in brittle rubber. There is a fear. In addition, the hydrogen atom couple | bonded with a silicon atom may be located in any of the molecular chain terminal and the middle of a molecular chain, and may be located in both.

Examples of the organohydrogenpolysiloxane of the component (B) include 1,1,3,3-tetramethyldisiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, tris (hydrogendimethylsiloxy) methylsilane, Tris (hydrogendimethylsiloxy) phenylsilane, methylhydrogencyclopolysiloxane, methylhydrogensiloxane / dimethylsiloxane cyclic copolymer, trimethylsiloxy group-blocked methylhydrogenpolysiloxane at both ends, trimethylsiloxy group-blocked dimethylsiloxane at both ends Methyl hydrogen siloxane copolymer, both ends dimethyl hydrogen siloxy group-capped dimethyl polysiloxane, both ends dimethyl hydrogen siloxy group capped dimethyl siloxane methyl high Rogen siloxane copolymer, trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane copolymer, trimethylsiloxy group-blocked methylhydrogensiloxane / diphenylsiloxane / dimethylsiloxane copolymer, both-end trimethylsiloxy group-blocked Methylhydrogensiloxane / methylphenylsiloxane / dimethylsiloxane copolymer, both ends dimethylhydrogensiloxy group-blocked methylhydrogensiloxane / dimethylsiloxane / diphenylsiloxane copolymer, both ends dimethylhydrogensiloxy group-blocked methylhydrogensiloxane / dimethylsiloxane-methylphenylsiloxane copolymer, (CH _{3) 2} HSiO _1/2 units and (CH _{3) 3} SiO _1/2 units and SiO _4/2 Position and a copolymer, (CH ₃₎ a copolymer consisting of ₂ HSiO _1/2 units and SiO _4/2 units, and (CH _{3) 2} HSiO _1/2 units and SiO _4/2 units (C _{And a} copolymer comprising ₆ H ₅ ) SiO _3/2 units.

  The compounding amount of the organohydrogenpolysiloxane is 0.1 to 30 parts by mass, preferably 0.3 to 20 parts by mass with respect to 100 parts by mass of the component (A). If the amount is less than 0.1 parts by mass, the curing is insufficient and the gel is formed, and a rubber-like elastic cured product cannot be obtained. If the amount exceeds 30 parts by mass, the strength of the cured product and compression set resistance Is significantly reduced (compression set becomes large). For the same reason as described above, the molar ratio ((B ′) / (A ′)) of the silicon atom-bonded hydrogen atom (B ′) to the alkenyl group (A ′) of the component (A) is 0.3-5. 0.0, in particular in the range of 0.5 to 2.5.

Next, the inorganic filler of component (C) is used for the purpose of increasing the strength of the composition and adjusting the viscosity and hardness. As such, any fumed silica, precipitated silica, pulverized quartz, diatomaceous earth, alumina, zinc oxide, magnesium oxide, titanium oxide and the like that do not inhibit the curing reaction of silicone rubber may be used. Among these, fumed silica is preferable for the purpose of reinforcement, and a specific surface area of 50 to 350 m ² / g is preferable. A compounding quantity is 10 mass parts or less with respect to 100 mass parts of (A) component, Preferably it is 0.5-8 mass parts. If it exceeds 10 parts by mass, the compression set becomes high. For the purpose of adjusting viscosity and hardness, pulverized quartz and diatomaceous earth are suitable. In this case, the average particle size is 0.5 to 30 μm, preferably 1 to 20 μm. When the average particle size is smaller than 0.5 μm, the compression set becomes high, and when it is larger than 30 μm, the physical properties of rubber are remarkably deteriorated. Moreover, as a compounding quantity, it is 1-50 mass parts with respect to 100 mass parts of (A) component, Preferably it is 2-40 mass parts. If it is less than 1 part by mass, there is no effect in adjusting the viscosity and hardness, and if it exceeds 50 parts by mass, the physical properties of the rubber are greatly reduced. The average particle diameter can be determined as a cumulative weight average value (or median diameter) or the like using a particle size distribution measuring apparatus such as a laser diffraction method.

  These inorganic fillers include silane coupling agents or partial hydrolysates thereof, alkylalkoxysilanes or partial hydrolysates thereof, organic silazanes, titanate coupling agents, organopolysiloxane oils, hydrolyzable functional groups. It may be surface-treated with a contained organopolysiloxane or the like. In these treatments, the inorganic powder itself may be treated in advance, or may be performed at the time of mixing with oil.

  These inorganic fillers of component (C) may be mixed with components (A) and (B) at room temperature using a planetary mixer or kneader, or at a high temperature of 100 to 200 ° C. May be mixed.

  As the conductivity imparting material of component (D), conductive carbon black is preferably used. As the conductive carbon black, those commonly used in conductive rubber compositions can be used. For example, acetylene black, conductive furnace black (CF), super conductive furnace black (SCF), and extra conductive furnace black (XCF). And conductive channel black (CC), furnace black and channel black heat-treated at a high temperature of about 1,500 ° C., and the like.

Specifically, as acetylene black, electrified acetylene black (manufactured by Electrochemical Co., Ltd.), Shaunigan acetylene black (manufactured by Shaunigan Chemical Co., Ltd.), etc., and as conductive furnace black, Continex CF (manufactured by Continental Carbon) , Vulcan C (manufactured by Cabot Corp.), etc., Superconductive Furnace Black, Connexex SCF (Continental Carbon Corp.), Vulcan SC (Cabot Corp.), etc., Extra Conductive Furnace Black, Asahi HS-500 ( Asahi Carbon Co., Ltd.), Vulcan XC-72 (Cabot Co., Ltd.), etc., examples of the conductive channel black include Kourax L (Degussa Co., Ltd.), and Ketjen, a kind of furnace black. Rack EC and Ketchen black EC-600JD (manufactured by Ketchen Black International Co., Ltd.), and the like can also be used. Of these, acetylene black is particularly preferable, and the specific surface area is 30 to 120 m ² / g, preferably 35 to 100 m ² / g, and the iodine adsorption amount is 30 to 120 mg / g, preferably 40 to 100 mg / g. The DBP oil absorption is 100 to 200 ml / 100 g, preferably 120 to 180 ml / 100 g. Outside these ranges, the resistance may not be stable.

  The blending amount of the component (D) is such that the volume resistivity of the cured product of the silicone rubber composition is 10 kΩ · m or less, preferably 0.1 to 10 kΩ · m, particularly preferably 1 Ω · m to 1 kΩ · m. Amount.

  Specifically, the addition amount of the conductive carbon black is preferably 0.5 to 50 parts by mass, particularly 1 to 20 parts by mass with respect to 100 parts by mass of the component (A). If the addition amount is less than 0.5 parts by mass, desired conductivity may not be obtained, and if it exceeds 50 parts by mass, compression set may be deteriorated.

  (E) Component addition reaction catalysts include platinum black, platinous chloride, chloroplatinic acid, a reaction product of chloroplatinic acid and a monohydric alcohol, a complex of chloroplatinic acid and olefins, platinum bisacetoacetate, A palladium catalyst, a rhodium catalyst, etc. are mentioned. In addition, the compounding quantity of this addition reaction catalyst can be made into a catalyst quantity, and is 0.5-1,000 ppm with respect to the total amount of (A) and (B) component as a platinum group metal normally, Especially 1-500 ppm. Degree.

  The silicone rubber composition of the present invention further includes an addition reaction control agent such as an acetylene alcohol compound, a dispersant such as low molecular siloxane, titanate ester, silanol, for example diphenylsilanediol, iron oxide, cerium oxide, iron octylate. A heat resistance improver such as, various carbon functional silanes for improving adhesiveness and moldability, halogen compounds for imparting flame retardancy, and the like may be added and mixed within a range not impairing the object of the present invention.

  The viscosity of the silicone rubber composition of the present invention is preferably 10 to 100 Pa · s, particularly 20 to 80 Pa · s at 25 ° C. If it is less than 10 Pa · s, the viscosity is too low to make molding difficult, and if it exceeds 100 Pa · s, resistance variation due to molding becomes large.

In the present invention, the curable silicone rubber composition has 30 seconds ≦ T10 ≦ 120 seconds, where 10% curing time at 120 ° C. is T10 (seconds) and 90% curing time is T90 (seconds), and 20 seconds ≦ T90−T10 ≦ 120 seconds are satisfied. Here, T10 and T90 are each a curast meter (manufactured by Nigo Shoji Co., Ltd., measured for 6 minutes with a curast meter V type), and indicate 10% curing time and 90% curing time of MAX torque.
T10 is 30 seconds or longer and 120 seconds or shorter, preferably 40 seconds or longer and 100 seconds or shorter. If it is less than 30 seconds, adhesion to the surface layer becomes insufficient, and if it exceeds 120 seconds, the process time becomes long, which is economically disadvantageous. T90-T10 is an important factor indicating the speed of the curing reaction, and needs to be 20 seconds or longer and 120 seconds or shorter, preferably 25 seconds or longer and 100 seconds or shorter, more preferably 30 seconds or longer and 90 seconds or shorter. is there. If it is less than 20 seconds, the end of the curing reaction is too fast and the adhesion to the surface layer becomes insufficient, and if it is 120 seconds or more, the molding cycle until demolding becomes long, which is economically disadvantageous.

  The above curability is particularly controlled in silicone rubber compositions by controlling the addition amount of an addition reaction catalyst and / or an addition reaction control agent such as acetylene alcohol, and the molar ratio of silicon atom bonded hydrogen atoms to silicon atom bonded alkenyl groups in the composition. As a alkenyl group-containing compound, a small amount of a compound containing many alkenyl groups in one molecule (for example, a non-silicon compound or a siloxane compound containing 50 mol% or more of alkenyl groups with respect to silicon atoms). It can be achieved by means such as blending.

  The molding method of the silicone rubber composition according to the present invention includes injection molding, injection molding, coating, and the like, and the curing conditions are 100 to 300 ° C., preferably 110 to 200 ° C., more preferably 120 to 160 ° C. A temperature range of 1 minute to 3 hours, preferably 10 minutes to 2 hours is suitably employed. Further, for the purpose of lowering compression set, reducing low molecular siloxane components, etc., post-curing for about 30 minutes to 70 hours in an oven at 120 to 250 ° C., preferably 150 to 220 ° C. A secondary cure may be performed.

  The cured product (silicone rubber layer) of the silicone rubber composition of the present invention has a volume resistivity of 10 kΩ · m or less, preferably 0.1Ω · m to 10 kΩ · m, more preferably 1Ω · m to 1 kΩ. -M. If it is greater than 10 kΩ · m, the electrical resistance is not stable and a clear image cannot be obtained. If it is less than 0.1 Ω · m, the blending amount of the conductivity-imparting agent may be too large to obtain roll durability. Further, the tensile strength of the cured product is preferably 2.0 MPa or more, particularly preferably 2.5 MPa or more. If it is less than 2.0 MPa, the durability as a roller may be insufficient. The cured product of the silicone rubber composition of the present invention has a compression set [25% compression, 180 ° C. × 22 hours] of usually 10% or less, preferably 8% or less, more preferably 6% or less, If the compression set is too large, the roller durability may be inferior.

  Furthermore, it is desirable that the hardness of the silicone rubber layer by durometer type A is 20 to 60, more preferably 30 to 50. If the hardness is too low, the acceptance and transfer performance of the toner as a conductive roller may be reduced, and if it is too high, the toner may be damaged.

Roller conductive silicone rubber composition of the present invention, charging roller, developing roller, paper feed rolls, the toner conveying roll, a roll application of an electrophotographic apparatus such as a transfer roll, or in particular the developing roll, charging roll and transfer roll As a roll selected from the above, it is particularly suitable for a developing roll.

  In addition, the silicone rubber composition of this invention needs to coat | cover the hardened | cured material layer on a metal core, and to provide the surface layer which consists of resin in the circumference | surroundings for these rolls. Examples of such resins include polyamide resins, polyimide resins, urethane resins, polyester resins, phenol resins, and fluorine resins, and those coated with a resin having a urethane bond and / or an amide bond are particularly preferable. When these resin layers are provided on the silicone rubber layer, the silicone rubber layer may be surface-treated with UV, plasma, excimer laser, or various primers and adhesives may be used. As a method for forming the surface layer resin, there are various coating methods such as bar coating, spray coating, and ring coating, and injection molding or dipping.

  In addition, although the thickness of a silicone rubber layer is selected suitably, it is 0.5-50 mm normally, especially 1-30 mm, and the thickness of a surface layer shall be the range of 1-1000 micrometers, especially 5-500 micrometers. Is preferred.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example. In addition, in the following example, a part shows a mass part.

[Example 1]
95 parts of dimethylpolysiloxane blocked at both ends with dimethylvinylsiloxy groups (degree of polymerization: 300), dimethylpolysiloxane having an average of 9 silicon-bonded vinyl groups in one molecule and blocked at both ends with trimethylsiloxy groups (Polymerization degree 100, vinyl value 1.2 × 10 ⁻³ mol / g) 5 parts, hydrophobized fumed silica having a specific surface area of 110 m ² / g (manufactured by Nippon Aerosil Co., Ltd., R-972) 2 parts, 25 parts of pulverized quartz having an average particle diameter of 5 μm, 4.0 parts of acetylene black having a specific surface area of 70 m ² / g, iodine adsorption of 92 mg / g and DBP oil absorption of 160 ml / 100 g are put in a planetary mixer, After stirring for 30 minutes, the mixture was passed once through three rolls. This was returned to the planetary mixer, and as a crosslinking agent, 4.2 parts of methyl hydrogen polysiloxane having a Si—H group at both ends and side chains (polymerization degree 20, Si—H group amount 0.0045 mol / g), As a reaction control agent, 0.05 part of ethynylcyclohexanol and 0.1 part of a platinum catalyst (Pt concentration 1%) were added, and a composition obtained by continuing stirring for 15 minutes was designated as a silicone rubber composition (1). The viscosity of this composition (1) at 25 ° C. is 62 Pa · s, and the curability at 120 ° C. with a curastometer V type is T10 = 1 minute 10 seconds and T90 = 2 minutes 30 seconds. .
This silicone rubber composition (1) is press-cured at 150 ° C. for 5 minutes, further post-cured at 200 ° C. for 4 hours, and hardness (durometer type A) and tensile strength, volume resistance and compression permanent according to JIS K6249. Strain [25% compression, 180 ° C. × 22 hours] was measured. The results are shown in Table 1.

Next, primer No. 4 (manufactured by Shin-Etsu Chemical Co., Ltd.), an iron core shaft with a diameter of 6 mm and a length of 300 mm was installed at the center of the mold, and the silicone rubber composition (1) was injected around the core shaft, After curing at 140 ° C. for 30 minutes, it was removed from the mold and left in an oven at 200 ° C. for 4 hours to obtain a conductive roller elastic layer having a diameter of 14 mm and a rubber part length of 240 mm. A polyurethane resin layer having a thickness of about 20 μm was formed by dipping a urethane resin thereon, air drying, and heat treatment at 150 ° C. for 2 hours.
Two of these conductive rollers were prepared, overlapped at a weight of 1 kg, and subjected to a durability test at 30 rpm in an oven at 105 ° C. No abnormalities were found in the appearance of the roller even after a 200-hour continuous test.

[Example 2]
98 parts of dimethylpolysiloxane blocked at both ends with dimethylvinylsiloxy groups (degree of polymerization 300), dimethylpolysiloxane with both ends having an average of 6 silicon atom-bonded vinyl groups in one molecule blocked with trimethylsiloxy groups (Polymerization degree 50, vinyl value 1.6 × 10 ⁻³ mol / g) 2 parts, hydrophobized fumed silica having a specific surface area of 110 m ² / g (manufactured by Nippon Aerosil Co., Ltd., R-972) Planetary mixer with 0.5 parts, 10 parts of diatomaceous earth with an average particle size of 7 μm, 4.5 parts of acetylene black with a specific surface area of 39 m ² / g, iodine adsorption of 52 mg / g and DBP oil absorption of 140 ml / 100 g The mixture was stirred for 30 minutes and then passed once through three rolls. This was returned to the planetary mixer, and as a crosslinking agent, 3.5 parts of methyl hydrogen polysiloxane having a Si—H group at both ends and side chains (polymerization degree 20, Si—H group amount 0.0045 mol / g), As a reaction control agent, 0.05 part of ethynylcyclohexanol and 0.12 part of platinum catalyst (Pt concentration 1%) were added, and the composition obtained by continuing stirring for 15 minutes was designated as a silicone rubber composition (2). The viscosity of this composition (2) at 25 ° C. is 46 Pa · s, and the curability at 120 ° C. with a curastometer V type is T10 = 58 seconds and T90 = 1 minute 29 seconds.
This silicone rubber composition (2) is press-cured at 150 ° C. for 5 minutes, and further post-cured at 200 ° C. for 4 hours. According to JIS K6249, hardness (durometer type A), tensile strength, volume resistance and compression permanent Strain [25% compression, 180 ° C. × 22 hours] was measured. The results are shown in Table 1.

Next, primer No. 101A / B (manufactured by Shin-Etsu Chemical Co., Ltd.) was applied and baked at 150 ° C for 30 minutes, an iron core shaft with a diameter of 8 mm and a length of 300 mm was placed in the center of the mold, and the above silicone was placed around the core shaft After injecting the rubber composition (2) and curing at 120 ° C. for 45 minutes, the rubber composition is removed from the mold and left in an oven at 220 ° C. for 2 hours to obtain a conductive roller elastic layer having a diameter of 18 mm and a rubber part length of 240 mm. It was. An amide resin was spray-coated thereon, air-dried, and then a polyamide resin layer having a thickness of about 10 μm was formed by heat treatment at 130 ° C. for 2 hours.
Two of these conductive rollers were prepared, overlapped with a load of 2 kg, and subjected to a durability test at 45 rpm in an oven at 120 ° C. Even after 300 hours of continuous testing, no abnormality was observed in the appearance of the roller.

[Comparative Example 1]
Hydrophobized fumed silica (Nippon Aerosil Co., Ltd., R-972) having 100 parts of dimethylpolysiloxane (polymerization degree 300) blocked at both ends with dimethylvinylsiloxy groups and a specific surface area of 110 m ² / g ) 0.2 parts, 25 parts of pulverized quartz with an average particle size of 12 μm, 4.0 parts of acetylene black having a specific surface area of 70 m ² / g, iodine adsorption of 92 mg / g and DBP oil absorption of 160 ml / 100 g The mixture was stirred for 30 minutes and then passed once through three rolls. This was returned to the planetary mixer, and as a crosslinking agent, 4.0 parts of methyl hydrogen polysiloxane having a Si—H group at both ends and side chains (polymerization degree 20, Si—H group amount 0.0045 mol / g), As a reaction control agent, 0.05 part of ethynylcyclohexanol and 0.15 part of platinum catalyst (Pt concentration: 1%) were added, and the composition obtained by continuing stirring for 15 minutes was designated as a silicone rubber composition (3). The viscosity of this composition (3) at 25 ° C. is 59 Pa · s, and the curability at 120 ° C. with a curastometer V type is T10 = 48 seconds and T90 = 1 minute 6 seconds.
This silicone rubber composition (3) is press-cured at 150 ° C. for 5 minutes, and further post-cured at 200 ° C. for 4 hours. According to JIS K6249, hardness (durometer type A), tensile strength, volume resistance and compression permanent Strain [25% compression, 180 ° C. × 22 hours] was measured. The results are shown in Table 1.

Next, primer No. 4 (manufactured by Shin-Etsu Chemical Co., Ltd.), an iron core shaft with a diameter of 6 mm and a length of 300 mm was installed in the center of the mold, and the silicone rubber composition (3) was injected around the core shaft, After curing at 140 ° C. for 30 minutes, it was removed from the mold and left in an oven at 200 ° C. for 4 hours to obtain a conductive roller elastic layer having a diameter of 14 mm and a rubber part length of 240 mm. A polyurethane resin layer having a thickness of about 20 μm was formed by dipping a urethane resin on this, followed by air drying and heat treatment at 150 ° C. for 2 hours.
Two of these conductive rollers were prepared, overlapped at a weight of 1 kg, and subjected to a durability test at 30 rpm in an oven at 105 ° C. After 120 hours, slight wrinkles were observed on the surface, and the surface stopped after 130 hours. When the roller was observed, peeling of the surface layer and rubber was observed at the end.

[Comparative Example 2]
98 parts of dimethylpolysiloxane blocked at both ends with dimethylvinylsiloxy groups (degree of polymerization 300), dimethylpolysiloxane with both ends having an average of 6 silicon atom-bonded vinyl groups in one molecule blocked with trimethylsiloxy groups (Polymerization degree 50, vinyl value 1.6 × 10 ⁻³ mol / g) 2 parts, hydrophobized fumed silica having a specific surface area of 110 m ² / g (manufactured by Nippon Aerosil Co., Ltd., R-972) Planetary mixer with 0.5 parts, 10 parts of diatomaceous earth with an average particle size of 7 μm, 4.5 parts of acetylene black with a specific surface area of 39 m ² / g, iodine adsorption of 52 mg / g and DBP oil absorption of 140 ml / 100 g The mixture was stirred for 30 minutes and then passed once through three rolls. This was returned to the planetary mixer, and as a crosslinking agent, 3.5 parts of methyl hydrogen polysiloxane having a Si—H group at both ends and side chains (polymerization degree 20, Si—H group amount 0.0045 mol / g), As a reaction control agent, 0.05 part of ethynylcyclohexanol and 0.22 part of platinum catalyst (Pt concentration 1%) were added, and the composition obtained by continuing stirring for 15 minutes was designated as a silicone rubber composition (4). The viscosity of this composition (4) at 25 ° C. is 46 Pa · s, and the curability at 120 ° C. with a curastometer V type is T10 = 27 seconds and T90 = 1 minute 18 seconds.
This silicone rubber composition (4) is press-cured at 150 ° C. for 5 minutes, and further post-cured at 200 ° C. for 4 hours. According to JIS K6249, hardness (durometer type A), tensile strength, volume resistance and compression permanent Strain [25% compression, 180 ° C. × 22 hours] was measured. The results are shown in Table 1.

Next, primer No. 101A / B (manufactured by Shin-Etsu Chemical Co., Ltd.) was applied and baked at 150 ° C for 30 minutes, an iron core shaft with a diameter of 8 mm and a length of 300 mm was placed in the center of the mold, and the above silicone was After injecting the rubber composition (4) and curing at 120 ° C. for 45 minutes, the rubber composition (4) is removed from the mold and left in an oven at 220 ° C. for 2 hours to obtain a conductive roller elastic layer having a diameter of 18 mm and a rubber part length of 240 mm. It was. An amide resin was spray coated thereon, and after air drying, a polyamide resin layer having a thickness of about 10 μm was formed by heat treatment at 130 ° C. for 2 hours.
Two of these conductive rollers were prepared, overlapped with a load of 2 kg, and subjected to a durability test at 45 rpm in an oven at 120 ° C. After 250 hours, wrinkles were observed on the surface, and the surface stopped after 260 hours. When the roller was observed, peeling of the surface layer and the rubber layer was observed over the entire roller.

Claims (12)

A conductive roller having a conductive metal core, a silicone rubber elastic layer provided around the metal core, and a surface layer made of resin around the metal core, wherein the silicone rubber elastic layer comprises:
(A) The alkenyl group content containing an alkenyl group bonded to at least two silicon atoms in one molecule is 1.0 × 10 ⁻⁶ mol / g to 5.0 × 10 ⁻³ mol / g, It is an organopolysiloxane which is liquid at room temperature (25 ° C.) having a polystyrene-equivalent weight average degree of polymerization of 100 to 1,000 in gel permeation chromatography analysis , and 0.5 to 20% by mass of the organopolysiloxane is containing vinyl group bonded to 4-50 silicon atoms in a molecule, Ru vinyl group content of ^{3.0 × 10 -4 mol / g~1.4 ×} 10 -2 mol / g der polymerization 100 parts by mass of an organopolysiloxane having a degree of 4 to 600,
(B) containing hydrogen atoms bonded to at least two silicon atoms (Si-H groups) in a molecule, Si-H group content of Ru 0.001~0.017mol / g Der organohydrogen 0.1 to 30 parts by mass of polysiloxane,
(However, the Si-H group in the component (B) relative to the alkenyl group in the component (A)
Of the molar ratio of 0.3 to 5.0)
(C) 0.5-50 parts by mass of an inorganic filler,
(D) Conductivity-imparting material selected from conductive carbon black having a specific surface area of 30 to 120 m ² / g, iodine adsorption of 30 to 120 mg / g, and DBP oil absorption of 100 to 200 ml / 100 g Volume resistance of cured product In an amount of 10 kΩ · m or less,
(E) addition reaction catalyst catalyst amount,
(F) When the 10% curing time at 120 ° C. of the composition is T10 (seconds) and the 90% curing time is T90 (seconds), T10 and T90 are 30 seconds ≦ T10 ≦ 120 seconds and 20 seconds ≦ T90, respectively. -T10 as an essential component an addition reaction control agent in an amount to ≦ 120 seconds state, and are not viscosity curing the curable silicone rubber composition of 10-100 Pa · s at 25 ° C., the silicone rubber composition was 5 minutes press cured at 0.99 ° C., the volume resistivity when the 4 hours post-cured at 200 ° C. is the 0.1Ω · m~10kΩ · m, 20-60 der Rukoto hardness by durometer type a Characteristic conductive roller. (F) the amount of component is an amount to T10 of 58 seconds ≦ T10 ≦ 70 seconds at 120 ° C. of the composition according to claim 1 conductive roller according. The conductive roller according to claim 1 or 2 , wherein the blending amount of the component (F) is such that T90 at 120 ° C of the composition is 30 seconds ≤ T90-T10 ≤ 90 seconds. Conductive carbon black, conductive roller of any one of claims 1 to 3, wherein the acetylene black. Conductive roller of any one of claims 1-4, wherein the tensile strength of the silicone rubber layer is not less than 2.0 MPa. The conductive roller according to any one of claims 1 to 5 , wherein the compression set of the silicone rubber layer at 180 ° C for 22 hours (25%) is 10% or less. The conductive roller according to any one of claims 1 to 6 , wherein the resin forming the surface layer is a resin containing a urethane bond and / or an amide bond. Conductive roller, developing roller, charging roller and the conductive roller of any one of claims 1 to 7 are those selected from the transfer roll. Method for improving the adhesion between the silicone rubber elastic layer and the surface layer in a conductive roller having a conductive metal core, a silicone rubber elastic layer provided around the metal core, and a surface layer made of resin around the metal core A silicone rubber composition layer according to any one of claims 1 to 4 is formed on the core metal and cured at a temperature of 120 to 300 ° C for 1 minute to 3 hours. A method for improving adhesion between the silicone rubber elastic layer and the surface layer, wherein a rubber elastic layer is formed and a surface layer made of a resin is formed around the rubber elastic layer. The method according to claim 9 , wherein the silicone rubber composition is molded by any one of injection molding, injection molding, and coating. Furthermore, the method of Claim 9 or 10 which performs the postcure for 30 minutes-70 hours at 120-250 degreeC. The method according to any one of claims 9 to 11 , wherein the resin forming the surface layer is a resin containing a urethane bond and / or an amide bond.