JP5127368B2 - Method for producing electrophotographic member - Google Patents

Description

The present invention relates to a process for producing an electrophotographic member having a surface layer formed using a co computing agents.

  In electrophotographic apparatuses such as copying machines and laser beam printers, a charging member that uniformly charges the outer surface of the photosensitive member, and toner is supplied to the electrostatic latent image formed on the surface of the photosensitive member and developed as a toner image. A developing member and a transfer member for transferring the toner image to the recording material are provided. In addition, a fixing member for fixing the toner image on the recording material, a cleaning member for removing the toner remaining on the surface of the photoreceptor after the transfer, and the like are provided. Of these members, particularly a member that needs to ensure a sufficient contact nip with the photoreceptor has a support and a conductive elastic layer provided on the support. Such a conductive elastic layer is formed from a rubber component such as urethane rubber. This type of rubber component contains a large amount of low molecular weight components, and the low molecular weight components bleed out and contaminate the surface of the photoreceptor. There is. In order to suppress bleed-out of low molecular weight components from the conductive elastic layer, a surface layer having a higher elastic modulus than the conductive elastic layer is provided on the conductive elastic layer.

  Specifically, it has been reported that a coating liquid using a sol-gel method is cured and applied to a transfer and / or fixing member (Patent Document 1). In synthesizing this coating solution, it is described that a catalyst such as hydrochloric acid, phosphoric acid, acetic acid or the like is used as appropriate in order to accelerate the hydrolysis reaction of the alkoxide.

  It has also been reported that a coating solution using a sol-gel method is cured and applied to a surface layer of an electrophotographic conductive roll, a conductive belt or the like. In this coating solution, it is described that a catalyst such as hydrochloric acid, phosphoric acid, acetic acid or the like is appropriately used in order to promote the hydrolysis reaction of the alkoxide.

  However, in order to make the composition contained in the coating solution uniform and free of residual unreacted monomer, pH adjustment during synthesis is very important. Inherently, the stability of the synthesis may be affected by changes in the pH of the raw material of the hydrolyzable silane compound itself or the pH of the entire mixture due to the combination thereof. In order to adjust the reaction rate, stability, etc. during synthesis, conventionally, pH adjustment during synthesis has been performed using hydrochloric acid, phosphoric acid, acetic acid, etc., but when such acids are used, the reaction is rapid. The molecular weight of the polysiloxane may become too large. Furthermore, it becomes difficult to dissolve in the solvent used by the polysiloxane itself, and white turbidity or phase separation may occur. When a coating film is formed using such a coating agent, coating unevenness, streaks, etc. occur, and the appearance of the member appears as it is in the image, and a non-uniform image may be formed. Further, when the synthesis is carried out by adjusting the alkalinity, the solution after synthesis is uniform at first glance, but a large amount of unreacted alkoxide monomer may remain. For this reason, the dehydration / condensation reaction of the residual monomers with time progresses, the viscosity increases with time, and a problem may arise in stability during storage as a coating solution.

Even if it is used immediately after synthesis to form a coating film, the residual monomer tends to re-aggregate from the wet state after coating to the curing and drying process, resulting in coating unevenness, coating streaks, etc., affecting image formation. Tend to affect.
JP 2002-038093 A JP 2002-080785 A

The subject of this invention is providing the manufacturing method of the member member for electrophotography in which the surface layer which suppressed coating unevenness, coating stripes, etc. was formed.

The present invention relates to a method for producing an electrophotographic member comprising the following steps (1), (2), (3) and (4):
(1) A hydrolyzable silane compound (A) containing a compound represented by the following formula (1), an alcohol (B), and carbonated water (C) having a pH of 4.5 to 6.5 are mixed, Adjusting the pH to 5.0 ≦ pH ≦ 6.4 by the amount of carbonated water (C) to create a mixture;
(2) The mixture is heated to reflux, and a polysiloxane having a weight average molecular weight (Mw) of 4.0 or more and 4.5 or less in a common logarithm is obtained by a dehydration / condensation reaction of the hydrolyzable silane compound (A). Producing a polysiloxane solution;
(3) adding a photopolymerization initiator (D) to the polysiloxane solution to prepare a coating agent; and
(4) A step of forming a coating layer of the coating agent on the surface of the conductive elastic layer provided on the support and irradiating the coating layer with active energy rays to form a surface layer.

(Wherein R ¹¹ , R ¹² Independently represents a saturated or unsaturated monovalent hydrocarbon group, Z ¹¹ Represents a divalent organic group, Rc ¹¹ Represents an organic group containing an epoxy group, d represents an integer of 0 to 2, e represents an integer of 1 to 3, and d + e = 3. )

ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of the member for electrophotography in which the surface layer which suppressed the coating nonuniformity, the coating stripe, etc. was formed can be provided.

Method for producing a coating agent according to the present invention, the step (1), (2), having a (3).

  In the step (1), the hydrolyzable silane compound (A), the alcohol (B), and the carbonated water (C) are mixed, and the pH is adjusted to 5.0 ≦ pH ≦ 6.4 depending on the mixed amount of the carbonated water (C). It is the process of preparing to a mixture by adjusting.

The hydrolyzable silane compound (A) used in the step (1) forms a polysiloxane by dehydration and condensation, and contains a compound represented by the formula (1) having a cationically polymerizable functional group. To do .

In the formula, R ¹¹ and R ¹² independently represent a saturated or unsaturated monovalent hydrocarbon group, Z ¹¹ represents a divalent organic group, and Rc ¹¹ represents an organic group containing an epoxy group. D represents an integer of 0 to 2, e represents an integer of 1 to 3, and d + e = 3.

In the formula (1), examples of the saturated or unsaturated monovalent hydrocarbon group independently represented by R ¹¹ and R ¹² include an alkyl group, an alkenyl group, and an aryl group. Among these, a C1-C3 linear or branched alkyl group is preferable, and a methyl group and an ethyl group are more preferable. In the formula (1), R ¹¹ is d (0 to 2), R ¹² is e (1 to 3), and the sum of R ¹¹ and R ¹² is d + e = 3. It is preferable that e is 3. In addition, when there are a plurality of R ¹¹ and R ¹² in the formula (1), they may be the same or different.

Specific examples of the divalent organic group represented by Z ¹¹ in formula (1) include an alkylene group and an arylene group. Among these, an alkylene group having 1 to 6 carbon atoms is preferable, and an ethylene group is more preferable.

In the formula (1), as the organic group containing an epoxy group represented by Rc ^11, Rue epoxy group to produce an oxyalkylene group by cleavage, it has easy availability, ease of reaction control. When the hydrolyzable silane compound (A) has an organic group containing an epoxy group, it is possible to form a cross-link between the produced polysiloxanes and improve the strength of the coating film.

  Specifically as a compound represented by Formula (1), the following can be mentioned, for example. Glycidoxypropyltrimethoxysilane (1-1), glycidoxypropyltriethoxysilane (1-2), epoxycyclohexylethyltrimethoxysilane (1-3), epoxycyclohexylethyltriethoxysilane (1-4). These can be used alone or in combination of two or more.

  Moreover, it is preferable that the compound represented by Formula (2) is included as a hydrolysable silane compound (A). By containing the compound represented by the formula (2), it is possible to reduce adhesion of a deposit on the surface of the coating film, for example, a toner or an external additive.

In the formula, R ²¹ and R ²² independently represent an unsubstituted or substituted alkyl group, Z ²¹ represents a divalent organic group, and Rp ²¹ represents a C 1-11 perfluoroalkyl. Indicates a group. f represents any integer of 0 to 2, g represents any integer of 1 to 3, and f + g = 3.

In formula (2), the alkyl group independently represented by R ²¹ and R ²² is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group. In formula (2), R ²¹ is f (0 to 2), R ²² is g (1 to 3), and the sum of R ²¹ and R ²² is f + g = 3. It is preferable that g is 3. Further, when there are a plurality of R ²¹ and R ²² in the formula (2), they may be the same or different.

In formula (2), specific examples of the divalent organic group represented by Z ²¹ include an alkylene group and an arylene group. Among these, an alkylene group having 1 to 6 carbon atoms is preferable, and an ethylene group is more preferable.

Wherein (2), as the perfluoroalkyl group having 1 to 11 carbon atoms represented by Rp ^21, from the viewpoint of processability, it is preferably a linear perfluoroalkyl group of 6-31 carbon atoms.

Specifically as a compound represented by Formula (2), the following can be mentioned, for example.
(2-1): CF ₃ — (CH ₂ ) ₂ —Si— (OR) ₃
(2-2): F (CF ₂ ) ₂ — (CH ₂ ) ₂ —Si— (OR) _{3
(2-3): F (CF 2} ) 4 - (CH 2) 2 -Si- (OR) 3 (2-3)
_{(2-4): F (CF 2} ) 6 - (CH 2) 2 -Si- (OR) 3 (2-4)
(2-5): F (CF ₂ ) ₈ — (CH ₂ ) ₂ —Si— (OR) ₃ (2-5)
(2-6): F (CF ₂ ) ₁₀ — (CH ₂ ) ₂ —Si— (OR) ₃
R in the above (2-1) to (2-6) represents a methyl group or an ethyl group. Among these, (2-4) to (2-6) are more preferable. The compound represented by Formula (2) can be used 1 type or in combination of 2 or more types, and (2-4) to (2-6) are particularly preferably used in combination.

Further, examples of the compound represented by the formula (2), it is preferable that the number of carbon atoms contained in Rp ²¹ is used in combination different. As the compound represented by the formula (2), those having Rp ²¹ of n _A (n _A is an integer of 6 to 31) and carbon number n _B (n _B is an integer of 6 to 31 and n _B ≠ n _A ), The resulting polysiloxane has perfluoroalkyl groups with different carbon numbers. The perfluoroalkyl group tends to be oriented toward the surface in the polysiloxane coating film, and perfluoroalkyl groups having different carbon numbers are oriented on the coating film surface. Polysiloxane coatings containing perfluoroalkyl groups with different carbon numbers have a higher fluorine atom density near the coating surface than polysiloxane coatings containing only a single carbon perfluoroalkyl group. The surface free energy becomes lower. For this reason, when a member having such a coating film is repeatedly used for a long period of time, it is possible to reduce the deposits on the surface of the member, for example, toner and external additives.

  Moreover, it is preferable that the compound represented by Formula (3) is included as a hydrolysable silane compound (A). The compound represented by the formula (3) has a function of adjusting physical properties such as surface charge amount.

In the formula, R ³¹ represents an unsubstituted or phenyl-containing alkyl group or an unsubstituted or alkyl-containing aryl group, and R ³² represents a saturated or unsaturated monovalent hydrocarbon group. a represents an integer of 0 to 3, b represents an integer of 1 to 4, and a + b = 4.

In formula (3), the unsubstituted or phenyl-containing alkyl group represented by R ³¹ is preferably a linear alkyl group having 1 to ²¹ carbon atoms. Also shown is R ^31, as the aryl group having an unsubstituted or alkyl group, an unsubstituted or phenyl group having a straight chain alkyl group having 1 to 21 carbon atoms are preferred. Examples of the saturated or unsaturated monovalent hydrocarbon group represented by R ³² include an alkyl group, an alkenyl group, and an aryl group. Among these, a C1-C3 linear or branched alkyl group is preferable, and a methyl group, an ethyl group, and an n-propyl group are more preferable. In the formula (3), R ³¹ is a (0 to 3) and R ³² is b (1 to 4), and the sum of R ³¹ and R ³² is a + b = 4. a is preferably an integer of 1 to 3, including the case where it is used in combination with the compound represented by Formula (2), more preferably 1, and b is a compound represented by Formula (2). Including the case where it is used together, an integer of 1 to 3 is preferable, and 3 is more preferable. When a plurality of R ²¹ and R ²² are present in the formula (3), they may be the same or different.

In formula (3), it is preferable that one R ³¹ out of a R ³¹ is a linear alkyl group having 1 to ²¹ carbon atoms. The carbon number of the linear alkyl group of R ³¹ is n ₁ (n ₁ is an integer of _{1 to} ²¹ ), and the carbon number of Rp ²¹ in formula (2) is n ₂ (n ₂ is an integer of ₁ to 31). ), It is preferable that n ₂ −1 ≦ n ₁ ≦ n ₂ +1. The alkyl group represented by R ^{31 of the} compound represented by formula (3) is oriented toward the surface of the electrophotographic member in the same manner as the perfluoroalkyl group represented by Rp ²¹ in the compound represented by formula (2). Tend to. If n ₁ ≦ n ₂ +1, the compound represented by the above formula (2) can be inhibited from inhibiting the effect of the perfluoroalkyl group represented by Rp ²¹ . On the other hand, if n ₂ −1 ≦ n ₁ , in the charging member to which the obtained coating agent is applied, the details of the reason are unknown, but it is possible to suppress the occurrence of ghosts due to poor charging. Ghost refers to a phenomenon in which when a halftone image is output, a high-density image such as characters or black graphics output immediately before the halftone image is output as a slight afterimage in the halftone image.

  Specifically as a compound represented by Formula (3), the following can be mentioned, for example. Tetramethoxysilane (3-1), tetraethoxysilane (3-2), tetrapropoxysilane (3-3), methyltrimethoxysilane (3-4), methyltriethoxysilane (3-5), methyltripropoxy Silane (3-6). Ethyltrimethoxysilane (3-7), ethyltriethoxysilane (3-8), ethyltripropoxysilane (3-9), propyltrimethoxysilane (3-10), propyltriethoxysilane (3-11), Propyltripropoxysilane (3-12). Hexyltrimethoxysilane (3-13), hexyltriethoxysilane (3-14), hexyltripropoxysilane (3-15), decyltrimethoxysilane (3-16), decyltriethoxysilane (3-17), Decyltripropoxysilane (3-18). Phenyltrimethoxysilane (3-19), phenyltriethoxysilane (3-20), phenyltripropoxysilane (3-21), diphenyldimethoxysilane (3-22), diphenyldiethoxysilane (3-23).

The compound represented by the formula (3) can be used alone or in combination of two or more, and in particular, it is possible to use a combination of R ³¹ showing an alkyl group and a phenyl group. preferable. Alkyl group segregated on the surface of the coating film tends high-impact given to the surface properties, for example, charging the first lap and the charging second round and subsequent saturation potential of the photoconductor (dark potential V _D1, V _D2) If a potential difference occurs between the two, a ghost may be generated. By using a combination of those in which R ³¹ represents a phenyl group, ghost can be suppressed.

As the hydrolyzable silane compound (A), the molar ratio (M _C ) of the compound (M _C ) represented by the formula (1) and the total (M ₁ ) of the compounds represented by the formula (2) and the formula (3). : M ₁ ) is preferably used in the range of 10: 1 to 1:10.

Furthermore, when the compound represented by Formula (1) and Formula (2) is used as the hydrolyzable silane compound (A), these compounds are preferably used in the following ranges. The compound represented by the formula (1) contains an organic group (epoxy group) containing an epoxy group represented by Rc ¹¹ in a range of 5.0 to 70.0% by mass relative to the total mass of the polysiloxane. It is preferable that the ratio is small. The compound represented by formula (2) is a perfluoroalkyl group represented by Rp ^21, relative to the total mass of polysiloxane is in proportions such as are contained in the range of 5.0 to 50.0 wt% It is preferable. Moreover, it is preferable to contain in the range which the siloxane part of the compound represented by Formula (1) and Formula (2) becomes the range of 20.0-90.0 mass% with respect to the polysiloxane total mass. .

Moreover, when the compound represented by Formula (1), Formula (2), and Formula (3) is used as the hydrolyzable silane compound (A), these compounds are preferably used in the following ranges. In the compound represented by the formula (1), an organic group (epoxy group) containing an epoxy group represented by Rc ¹¹ is contained in a range of 5.0 to 30.0% by mass with respect to the total mass of the polysiloxane. It is preferable that the ratio is small. The compound represented by formula (2) is a perfluoroalkyl group represented by Rp ^21, relative to the total mass of polysiloxane is in proportions such as are contained in the range of 5.0 to 50.0 wt% It is preferable. When R ³¹ is an alkyl group, the compound represented by the formula (3) contains an alkyl group in the range of 5.0 to 30.0% by mass with respect to the total mass of the polysiloxane. It is preferable that it is a ratio which is contained in 5.0-60.0 mass%. Moreover, it contains in the range from which the siloxane part of the compound represented by Formula (1), Formula (2), Formula (3) will be in the range of 20.0-80.0 mass% with respect to polysiloxane total mass. It is preferred that

  The alcohol (B) used in the step (1) is used for adjusting the concentration during synthesis. Examples of the alcohol (B) include alcohols such as ethanol and 2-butanol. The amount of the alcohol (B) used is a range in which a dehydration / condensation reaction of the hydrolyzable silane compound (A) can be efficiently and gently advanced to reduce unreacted monomers and a polysiloxane having a desired molecular weight can be obtained. It is. Specifically, the usage-amount of alcohol (B) is adjusted so that the density | concentration of the hydrolysable silane compound (A) in the mixture obtained at a process (1) may be 20-40 mass%. If the density | concentration of all the hydrolysable silane compounds (A) is 20 mass% or more, it can suppress that a reaction probability becomes low and can suppress that a residual monomer becomes large. If it is 40 mass% or less, control of reaction can be performed more easily.

  The carbonated water (C) used in the step (1) promotes the dehydration / condensation reaction of the hydrolyzable silane compound (A) in a mild state to reduce the residual monomer. It is preferable to use a solution in which the amount of carbon dioxide dissolved in water is changed and the pH is adjusted to 4.5 to 6.5, preferably 5.0 to 6.0. As the usage-amount of carbonated water (C), the quantity containing the carbonic acid of the mol number 1.0-2.0 times the mol number of the hydrolysis part of a hydrolysable silane compound (A) is preferable. If the number of moles of carbonic acid is 1.0 times or more, hydrolysis can proceed and the residual monomer can be reduced, and if it is 2.0 times or less, hydrolysis is slow. It is possible to suppress the increase in viscosity during long-term storage and the loss of stability.

  The following known methods can be used to adjust carbonated water. A method of forcibly dissolving carbon dioxide from a liquefied carbon dioxide cylinder in distilled water, purified water, ion-exchanged water, etc. under a constant temperature environment. A method in which a certain amount of dry ice is added to water and dissolved in an open state in a normal temperature and humidity environment (23 ± 3 ° C., 60 ± 10% RH).

  Here, the pH was first calibrated using two types of calibration solutions (pH = 7.0, pH = 4.0) using an electronic pH meter (Piccolo II: manufactured by Kanada Rika Kogyo Co., Ltd.). To a measured value measured in a normal temperature and humidity environment (23 ± 5 ° C., 60 ± 10% RH).

  In order to prepare the mixture by mixing the hydrolyzable silane compound (A), alcohol (B), and carbonated water (C), any of the addition methods thereof may be used. For example, while mixing hydrolyzable silane compound (A) and alcohol (B) and measuring pH, carbonated water (C) is added so that the pH is in the range of 5.0 ≦ pH ≦ 6.4. The mixing amount can be adjusted and added and stirred and mixed.

  By setting the pH of the mixture to 5.0 or more, a polysiloxane having an average molecular weight of 4.5 or less can be obtained in a common logarithmic display. If the average molecular weight is 4.5 or less in the common logarithm display of polysiloxane, white turbidity and phase separation of the polysiloxane solution caused by excessive molecular weight can be suppressed. For this reason, a good coating film can be formed using this, and the member for electrophotography which can suppress generation | occurrence | production of an image defect is obtained.

  Moreover, by setting the pH of the mixture to 6.4 or less, it is possible to obtain a polysiloxane having an average molecular weight of 4.0 or more in common logarithmic display. If the average molecular weight is 4.0 or more in the common logarithm display of polysiloxane, a polysiloxane solution with few residual monomers can be obtained.

  Step (2) is a step of preparing a polysiloxane solution by heating and refluxing the mixture prepared in step (1) to produce polysiloxane by dehydration / condensation reaction of the hydrolyzable silane compound (A). In the step (2), the hydrolyzable silane compound is hydrolyzed to produce silanol, and further condensed to produce polysiloxane. The mixture is preferably heated and refluxed at a temperature equal to or higher than the azeotropic temperature of alcohol (B) and carbonated water (C), preferably 60 ° C to 140 ° C, and more preferably 80 ° C to 120 ° C. . Under such conditions, most of the hydrolyzable silane compound (A) contained in the mixture is produced into polysiloxane by a dehydration / condensation reaction.

  Here, after the synthesis of polysiloxane, the amount of residual monomer in the polysiloxane solution to be prepared can be measured by the following method.

  About 2.000 to 3.000 g of the prepared polysiloxane solution is weighed (B) with a precision balance in an aluminum cup whose mass (A) has been measured in advance, and left in an oven at 160 ° C. for 15 minutes. Thereafter, the mass (C) is again measured with a precision balance, and the solid content contained in the polysiloxane solution is calculated by the following formula. When unreacted monomer is present, mass loss due to volatilization of the monomer occurs with the solvent contained in the polysiloxane solution and water generated by the dehydration / condensation reaction, and the mass loss is attributed to the residual monomer. The residual amount can be determined.

The monomer remaining in the polysiloxane solution obtained in the step (2) becomes extremely small when the pH of the mixture is adjusted to 5.0 ≦ pH ≦ 6.4 in the step (1). FIG. 2 shows the relationship between the solid content in the polysiloxane solution obtained in the step (2) and the pH of the mixture in the step (1). When the pH of the mixture in the step (1) is higher than 6.4, the solid content is rapidly lowered and the amount of residual monomer is increased. When the pH of the mixture in step (1) is lower than 5.0, the solid content is almost the theoretical value although not shown.

  Moreover, as polysiloxane produced | generated, it is preferable that a weight average molecular weight (Mw) is 4.0 or more and 4.5 or less in common logarithm display. If the polysiloxane has a weight average molecular weight (Mw) of 4.0 or more in the common logarithmic display, the content of residual monomer is small and thickening due to the progress of dehydration and condensation reaction of the monomer during storage can be suppressed. A coating agent having excellent stability can be obtained. If the polysiloxane is 4.0 or less in the common logarithm display, recoagulation occurs in the coating film even when the coating film is formed using the coating agent immediately after production without passing through the storage time. In some cases, uneven coating or streaks may occur, but the occurrence of such a situation can be suppressed.

  When the weight average molecular weight (Mw) of the polysiloxane is 4.5 or less in the common logarithm display, there are few monomers remaining in the polysiloxane solution, and a coating agent that can form a good coating film can be obtained.

The weight average molecular weight of the polysiloxane and (Mw), shows the relationship between solids in FIG. When the solid content in the polysiloxane solution is in the range of 6.6% by mass to 7.4% by mass, the weight average molecular weight (Mw) is 4.0 to 4.5 in the common logarithmic display. Siloxane can be obtained.

  As the weight average molecular weight of the polysiloxane, a value measured by the following measuring method can be adopted. HLC-8120GPC (manufactured by Tosoh Corporation) was used as the GPC apparatus. As the column, two TSKgel SuperH3000, TSKgel SuperH2000, and TSKgel SuperHM-M are connected and used. As the eluent, THF for high performance liquid chromatography is used, and the flow rate is 0.6 ml / min, the temperature is INLET 40 ° C., OVEN 40 ° C., and RI 40 ° C. The detector is RI, and the calibration curve is polystyrene (EasiCal PS-2). A sample is adjusted with THF for high performance liquid chromatography so that it may become 0.25 mass%.

  Step (3) is a step of adding a photopolymerization initiator (D) to the polysiloxane solution.

  The photopolymerization initiator (D) used in the step (3) is a functional group capable of cationic polymerization of the hydrolyzable silane compound (A) that is activated by irradiation with active energy rays and constitutes polysiloxane, for example, an epoxy group. Ring opening can be promoted and a bridge can be formed. The photopolymerization initiator (D) preferably contains a cationic polymerization initiator.

  The cationic polymerization initiator (D) is preferably selected according to the functional group contained in the polysiloxane. When the polysiloxane contains a cationically polymerizable epoxy group, it is preferable to use, for example, an onium salt of a Lewis acid that is activated by ultraviolet rays.

  Examples of other cationic polymerization initiators include a borate salt, a compound having an imide structure, a compound having a triazine structure, an azo compound, and a peroxide.

  Among various cationic polymerization initiators, aromatic sulfonium salts and aromatic iodonium salts are preferable from the viewpoints of sensitivity, stability, and reactivity. In particular, bis (4-tert-butylphenyl) iodonium salt, a compound represented by the following formula (Adekaoptoma-SP150: manufactured by Asahi Denka Kogyo Co., Ltd.),

Compound represented by the following formula (Irgacure 261: Ciba Specialty Chemicals)

Is preferred.

  The method for adding the photopolymerization initiator (D) to the polysiloxane solution is not particularly limited. For example, the light that activates the photopolymerization initiator (D) is blocked, and these are mixed and stirred. A coating agent can be obtained. The addition amount of the photopolymerization initiator is preferably in the range of 0.5 to 4.0% by mass based on polysiloxane as 100 because appropriate crosslinking can be formed.

  Thus, the coating agent obtained can adjust the viscosity of a polysiloxane solution using a suitable solvent for application property improvement. Examples of suitable solvents include alcohols such as ethanol and 2-butanol, ethyl acetate, methyl ethyl ketone, and mixtures thereof.

An electrophotographic member obtained by using the method for producing an electrophotographic member of the present invention has a surface layer formed by applying a coating agent obtained by the above-described method for producing a coating agent and irradiating active energy rays. Have.

  The surface layer is formed by applying the coating agent to form a coating film, and irradiating active energy rays to form a crosslink of polysiloxane. The application method may be any method, but application using a roll coater, dip application, ring application, or the like can be employed.

  As the active energy ray, ultraviolet rays are used to reduce heat generation, suppress expansion and contraction of the conductive elastic layer, follow not only during molding, but also change in the usage environment, and there are wrinkles and cracks in the surface layer. Generation | occurrence | production can be suppressed. In addition, the crosslinking can be formed in a short time, such as within 15 minutes, and deterioration of the electrical characteristics of the conductive elastic layer can be suppressed.

As the ultraviolet ray source, a high-pressure mercury lamp, a metal halide lamp, a low-pressure mercury lamp, an excimer UV lamp, or the like can be used, and among these, an ultraviolet ray source containing abundant light having an ultraviolet wavelength of 150 to 480 nm is preferable. The amount of UV irradiation can be adjusted by the irradiation time, lamp output, and the distance between the lamp and the object to be irradiated, and the irradiation amount can be graded within the irradiation time. Can be 5000 to 15000 mJ / cm ² . Amount ultraviolet rays can form sufficient crosslinking if 5000 mJ / cm ² or more, if 15,000 mJ / cm ² or less, and an increase in the surface free energy due to excessive oxidation during endurance toner or external additives It is possible to suppress adhesion and extension of charging failure. The cumulative amount of ultraviolet light can be calculated by the following formula.

UV integrated light quantity [mJ / cm ² ] = UV intensity [mW / cm ² ] × irradiation time [s]
Further, the ultraviolet integrated light quantity can be measured using an ultraviolet integrated light quantity meter (UIT-150-A or UVD-S254: manufactured by Ushio Electric Co., Ltd.) when ultraviolet irradiation is performed using a low-pressure mercury lamp. Moreover, when performing ultraviolet irradiation using an excimer UV lamp, it can measure using a UV integrated light meter (UIT-150-A and VUV-S172: Ushio Electric Co., Ltd. product).

As an example of an electrophotographic member obtained by using the method for producing an electrophotographic member of the present invention, a roller for an electrophotographic apparatus shown in FIG. 1 will be described below. The roller shown in FIG. 1 has a conductive elastic layer 102 on a support 101, and has the surface layer 103 on the conductive elastic layer.

  The support has conductivity, and examples of the material include iron, copper, stainless steel, aluminum, aluminum alloy, and nickel alloy. Further, the surface of the support may be subjected to a surface treatment such as a plating treatment within a range not impairing the conductivity for the purpose of imparting scratch resistance.

  The conductive elastic layer imparts elasticity to the developing roller in order to form a nip between the photoreceptors, and is formed of rubber, a thermoplastic elastomer, or the like. Examples of such rubbers include the following. Urethane rubber, silicone rubber, butadiene rubber, isoprene rubber, chloroprene rubber. Styrene-butadiene rubber, ethylene-propylene rubber, polynorbornene rubber, styrene-butadiene-styrene rubber, acrylonitrile rubber, epichlorohydrin rubber, alkyl ether rubber.

  Examples of the thermoplastic elastomer include styrene elastomers and olefin elastomers. Commercially available products such as Lavalon (manufactured by Mitsubishi Chemical Corporation) and Septon Compound (manufactured by Kuraray Co., Ltd.) can be used as the styrene elastomer. Examples of olefinic elastomers include Thermoran (Mitsubishi Chemical Co., Ltd.), Miralastomer (Mitsui Petrochemical Co., Ltd.), Sumitomo TPE (Sumitomo Chemical Co., Ltd.), Santoprene (Advanced Elastomer Systems Co., Ltd.), etc. Commercial products can be used.

Moreover, the electroconductivity can be set to a predetermined value by appropriately using a conductive agent in the conductive elastic layer. The electrical resistance of the conductive elastic layer can be adjusted by appropriately selecting the type and amount of the conductive agent, and the preferred range of the electrical resistance is 10 ² to 10 ⁸ Ω, and the more preferred range is 10 ³ to 10 ⁶ Ω.

  Examples of the conductive agent used in the conductive elastic layer include a cationic surfactant, an anionic surfactant, an amphoteric surfactant, an antistatic agent, and an electrolyte.

  Examples of the cationic surfactant include the following. Quaternary ammonium salts such as lauryltrimethylammonium, stearyltrimethylammonium, octadodecyltrimethylammonium, dodecyltrimethylammonium, hexadecyltrimethylammonium, and modified fatty acid dimethylethylammonium. Examples of the quaternary ammonium salt include perchlorate, chlorate, borofluoride, ethosulphate, and benzyl halide salts (such as benzyl bromide and benzyl chloride).

  Examples of the anionic surfactant include aliphatic sulfonate, higher alcohol sulfate ester salt, higher alcohol ethylene oxide addition sulfate ester salt, higher alcohol phosphate ester salt, higher alcohol ethylene oxide addition phosphate ester salt and the like. .

  Examples of the antistatic agent include nonionic antistatic agents such as higher alcohol ethylene oxide, polyethylene glycol fatty acid ester, and polyhydric alcohol fatty acid ester.

Examples of the electrolyte include salts (such as quaternary ammonium salts) of metals (Li, Na, K, etc.) belonging to Group 1 of the periodic table. Specific examples of the salts of metals belonging to Group 1 of the periodic table include LiCF ₃ SO ₃ , NaClO ₄ , LiAsF ₆ , LiBF ₄ , NaSCN, KSCN, and NaCl.

Furthermore, the following ionic conductive agents can be used as the conductive agent. Periodic table group 2 metals (Ca, Ba, etc.) salts (Ca (ClO ₄ ) ₂ etc.) and antistatic agents derived from them can react with isocyanates (primary amino groups, secondary amino groups, etc.) Having one or more groups having active hydrogen (hydroxyl group, carboxyl group, etc.). Complexes of these with polyhydric alcohols (1,4-butanediol, ethylene glycol, polyethylene glycol, propylene glycol, polyethylene glycol, etc.) or derivatives thereof. Complexes of these with monools (ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, etc.).

  As the conductive agent, conductive conductive agents such as ketjen black EC, acetylene black, carbon for rubber, carbon for color (ink) subjected to oxidation treatment, and pyrolytic carbon can be used. The following are mentioned as carbon for rubber | gum. Super Abrasion Furnace (SAF: Super Abrasion Resistance), Intermediate Super Abrasion Furnace (ISAF: Semi Super Abrasion Resistance), High Abrasion Furnace (HAF: High Abrasion Resistance). Fast Extruding Furnace (FEF: good extrudability), General Purpose Furnace (GPF: versatility), Semi Rein Forcing Furnace (SRF: medium reinforcement). Fine Thermal (FT: fine grain pyrolysis), Medium Thermal (MT: medium grain pyrolysis). Graphite such as natural graphite and artificial graphite. Metal oxides such as tin oxide, titanium oxide and zinc oxide, and metals such as nickel, copper, silver and germanium. Conductive polymers such as polyaniline, polypyrrole and polyacetylene.

  In addition, other fillers and crosslinking agents may be added to the conductive elastic layer. Examples of the filler include silica (white carbon), calcium carbonate, magnesium carbonate, clay, talc, zeolite, alumina, barium sulfate, and aluminum sulfate. Examples of the crosslinking agent include sulfur, peroxides, crosslinking aids, crosslinking accelerators, crosslinking acceleration aids, and crosslinking retarders.

  The hardness of the conductive elastic layer is preferably 70 degrees or more, and 73 degrees or more and 90 degrees or less with Asker C from the viewpoint of wear resistance and durability of a roller used in contact with the photoreceptor. It is more preferable.

FIG. 4 shows an example of an electrophotographic apparatus provided with a process cartridge to which an electrophotographic member obtained by using the electrophotographic member manufacturing method of the present invention is applied. The electrophotographic apparatus shown in FIG. 4 has a cylindrical photoreceptor 1 that is driven to rotate at a predetermined peripheral speed in the direction of an arrow about an axis 2. The photoreceptor may have a support, a photosensitive layer formed on the support, a charge injection layer, a surface layer, and the like.

  The surface of the rotationally driven photoconductor is uniformly charged to a predetermined positive or negative potential by the charging member 3, and then exposure light (not shown) output from exposure means (not shown) for slit exposure or laser beam scanning exposure. In response to the image exposure light 4, an electrostatic latent image corresponding to the target image is formed.

  When the surface of the photoreceptor 1 is charged by the charging member 3, a DC voltage or a voltage obtained by superimposing an AC voltage on the DC voltage is applied to the charging member 3 from a voltage applying unit (not shown).

  The electrostatic latent image formed on the surface of the photoreceptor 1 is supplied with a developer by a developing roller provided in the developing unit 5 and is reversely developed or normally developed to become a toner image. Next, the toner image on the surface of the photoreceptor 1 is transferred onto the transfer material such as paper conveyed between the photoreceptor 1 and the transfer roller 6 in synchronization with the rotation of the photoreceptor by a transfer bias applied to the transfer roller 6. Sequentially transferred to P.

  Examples of the developing means include jumping developing means, contact developing means, magnetic brush means, etc., but from the viewpoint of improving toner scattering properties, contact developing means is preferable. In the embodiments described later, contact developing means is used. Adopted.

  Moreover, as a transfer roller, what has the elastic resin layer adjusted to medium resistance on a support body can be used.

  The transfer material P onto which the toner image has been transferred is separated from the surface of the photoreceptor 1 and is introduced into the fixing unit 8, and is printed out as an image formed product (print, copy) on which the toner image is fixed. . In the case of the double-sided image forming mode or the multiple image forming mode, the image formed product is introduced into the recirculation transport mechanism and reintroduced into the transfer unit.

  The surface of the photoreceptor 1 after the transfer of the toner image is cleaned by removing the developer (toner) remaining after the transfer by a cleaning means 7 such as a cleaning blade, and further subjected to a charge removal process by pre-exposure light from the pre-exposure means. After that, it is repeatedly used for image formation. When the charging unit is a contact charging unit, pre-exposure is not always necessary.

  The photosensitive member 1, the charging member 3, the developing means 5, and the cleaning means 7 are integrated into a process cartridge 9, which is detachably attached to the electrophotographic apparatus main body using a guide means 10 such as a rail of the electrophotographic apparatus main body. . In addition to the above members, the cartridge can be appropriately selected from transfer means or the like, and can be detachably attached to the electrophotographic apparatus main body.

  Among these, the charging member, the developing roller, the transfer roller, the fixing unit, the cleaning blade, and the like can be the electrophotographic member having a surface layer formed using the coating agent.

Although the manufacturing method of the coating agent of this invention is demonstrated concretely in detail, the technical scope of this invention is not limited to these. The following numerical values indicate “% by mass”.
[Example 1]
[Preparation of conductive elastic layer]
The following were kneaded with a 6 L kneader for 20 minutes.
Medium-high nitrile [Product name: JSR N230SV (bonded acrylonitrile content 35.0%)
Mooney viscosity (ML _{1 + 4} 100 ° C.) 32, specific gravity 0.98, manufactured by JSR Corporation] 100 parts.
Color Carbon black as filler [trade name: # 7360SB, particle size 28nm, specific surface area by nitrogen adsorption 77m ² / g, DBP absorption amount 87100cm ³ / 100g, Tokai Carbon Co., Ltd.] 48 parts.
20 parts of calcium carbonate (trade name: Nanox # 30, manufactured by Maruo Calcium Co., Ltd.) as a filler.
48 parts made by Tokai Carbon Co., Ltd.
5 parts of zinc oxide.
1 part of stearic acid.

  Furthermore, tetrabenzyl thiuram disulfide [trade name: Sunseller TBZTD, manufactured by Sanshin Chemical Industry Co., Ltd.] 4.5 parts as a vulcanization accelerator, and 1.2 parts sulfur as a vulcanizing agent were added. A kneaded product I was obtained by kneading for 8 minutes.

  Next, a thermosetting adhesive containing metal and rubber (trade name: METALOC) in the region of a central portion of 231 mm of a cylindrical steel support having a diameter of 6 mm and a length of 252 mm (surface plated with nickel). N-33, manufactured by Toyo Chemical Laboratory Co., Ltd.) was applied. This was dried at a temperature of 80 ° C. for 30 minutes, and further dried at a temperature of 120 ° C. for 1 hour.

  Using a crosshead extruder, the kneaded product I and the support coated with the thermosetting adhesive and dried are simultaneously inserted, and the kneaded product I is extruded to the outer periphery of the support as a cylindrical shape with an outer diameter of 8.75 mm. The part was cut and vulcanized in a continuous heating furnace at a temperature of 160 ° C. for 1 hour to obtain a primary vulcanized product for the conductive elastic layer.

  Next, both ends of the conductive elastic layer portion (rubber portion) of the primary vulcanized product for the conductive elastic layer are cut, the surface of the conductive elastic layer portion is polished with a rotating grindstone, and the end diameter is 8.26 mm. A crown-shaped conductive elastic roller 1 having a central diameter of 8.5 mm was produced. This conductive elastic roller had a surface ten-point average roughness (Rz) of 6.0 μm, a deflection of 20 μm, and a hardness of 73 degrees (Asker C). Ten-point average roughness (Rz) was measured according to JISB6101.

  The shake was measured using a high-precision laser measuring machine LSM-430v manufactured by Mitutoyo Corporation. Specifically, the outer diameter is measured using the measuring device, and the difference between the maximum outer diameter value and the minimum outer diameter value is defined as the outer diameter difference run. This measurement is performed at five points, and the average of the five outer diameter difference shakes is measured. The value was the runout of the object to be measured.

[Preparation of surface layer]
Carbonated water was prepared. 1L of water [trade name: purified water (ion-exchanged water), manufactured by Kishida Chemical Co., Ltd.] was transferred to a polyethylene cup and opened in a normal temperature and humidity environment (23 ± 5 ° C, 60 ± 10% RH) For 96 hours. The pH of the carbonated water was 5.5.

The following were placed in a 500 ml eggplant flask, and a football-type rotor (full length 45 mm × diameter 20 mm) was added and mixed, followed by stirring at room temperature for 30 minutes to obtain a mixture. The pH of the mixture was 5.2.
(A) Glycidoxypropyltriethoxysilane (GPTES) [trade name: KBE-403, manufactured by Shin-Etsu Chemical Co., Ltd.] 27.44 g (0.099 mol) as a hydrolyzable silane compound.
(A) Phenyltriethoxysilane (PhTES) [trade name: KBE-103, manufactured by Shin-Etsu Chemical Co., Ltd.] 94.78 g (0.394 mol).
(A) Hexyltrimethoxysilane (HeTMS) [trade name: KBM-3063, manufactured by Shin-Etsu Chemical Co., Ltd.] 29.00 g (0.141 mol).
(A) Tridecafluoro-1,1,2,2-tetrahydrooctyltriethoxysilane (FTS-5) [trade name: SIT8175.0, manufactured by Gelest, Inc] 35.90 (0.070 mol).
(B) 48.18 g of ethanol.
(C) 45.64 g of the carbonated water (pH = 5.5).

Next, an oil bath set at 120 ° C. is placed on a stirrer with a temperature runaway prevention mechanism, and heated and refluxed at a rotational speed of 750 rpm for 20 hours, whereby a polysiloxane solution I-1 of a hydrolyzable silane compound condensate ( 28 mass% solid content) was obtained. The log (Mw) of this polysiloxane solution was 4.4.
Life Evaluation of Coating Agent Immediately after the synthesis of the obtained polysiloxane solution I-1, after being left for 3 months, the degree of condensation DC (Degree of Condensation) is calculated from the following formula by ²⁹ Si-NMR measurement, and the coating agent is stored. Stability was evaluated.

  As a sample preparation, 1.0 to 3.0 ml of a sample was filled into a 10 mm diameter Teflon sample tube, a relaxation reagent was added, and the mixture was sufficiently stirred and dissolved to perform measurement. Table 1 shows the measurement apparatus and measurement conditions.

Here, the attribution of T ₀ , T ₁ , T ₂ , T ₃ is as follows.

T ₀ : R—Si (OR) ₃ (−44 ppm)
T ₁ : R—Si (OR) ₂ (OSi≡) (−49 ppm)
(-63ppm)
T ₂ : R—Si (OR) ₁ (OSi≡) ₂ (−58 ppm)
(-71 ppm)
T ₃ : R—Si (OSi≡) ₃ (−66 ppm)
(-78ppm)

The DC is preferably 60 ≦ DC [%] ≦ 85. More preferably, 65 ≦ DC [%] ≦ 80. If DC <60, the residual monomer-derived T ₀ is large, the molecular weight of the polysiloxane is low, and coating unevenness and coating lines are likely to occur after coating. When DC> 85 in the initial stage or DC> 85 with time, the molecular weight of the polysiloxane increases, and the polysiloxane solution itself tends to become clouded or phase separated.

  The initial DC of the polysiloxane solution I-1 was 77.5, and the DC after 3 months was 84.2.

  2-butanol and ethanol were added to the polysiloxane solution I-1 at a mass ratio of 25 g / 10 g / 65 g to prepare a polysiloxane solution I-2 having a solid content of 7% by mass. The solid content was 7.12.

  To 100 g of this polysiloxane solution I-2, 0.35 g of an aromatic sulfonium salt [Adekaoptomer SP-150: manufactured by Asahi Denka Kogyo Co., Ltd.] as a photocationic polymerization initiator (D) is added. Dilution with ethanol gave coating agent 1 (solid content 2% by mass).

Next, the coating agent 1 was applied onto the conductive elastic layer of the conductive elastic roller I at a discharge rate of 0.008 ml / s, a ring portion speed of 30 mm / s, and a total discharge rate of 0.064 ml. Using a low-pressure mercury lamp manufactured by Harrison Toshiba Lighting Co., Ltd., the coating film was irradiated with ultraviolet light having a wavelength of 254 nm so that the integrated light amount was 8500 mJ / cm ² , cured, and dried for 2 to 3 seconds. A surface layer was formed to obtain a charging roller 1. It is considered that the glycidoxy group of glycidoxypropyltriethoxysilane was cleaved by the irradiation of ultraviolet rays, and a crosslinking reaction of polysiloxane occurred.

[Appearance evaluation of charging roller]
The appearance of the charging roller was evaluated according to the following criteria. The results are shown in Table 2.
A: Coating unevenness and streaks cannot be visually confirmed.
○: Coating unevenness and streaks that can hardly be visually confirmed.
Δ: Coating unevenness and streaks that can be visually confirmed only at the extreme part of the non-image area.
X: Coating unevenness and streaks that can be clearly confirmed in the image area visually.

[Example 2]
A polysiloxane solution II was prepared in the same manner as in Example 1 except that the mixture was prepared using the following, a coating agent 2 was prepared, a charging roller 2 was prepared, and the appearance was evaluated. The results are shown in Table 2.
(A) Glycidoxypropyltriethoxysilane (GPTES) [trade name: KBE-403, manufactured by Shin-Etsu Chemical Co., Ltd.] 23.95 g (0.086 mol) as a hydrolyzable silane compound.
(A) Phenyltriethoxysilane (PhTES) [trade name: KBE-103, manufactured by Shin-Etsu Chemical Co., Ltd.] 82.71 g (0.344 mol).
(A) Hexyltrimethoxysilane (HeTMS) [trade name: KBM-3063, manufactured by Shin-Etsu Chemical Co., Ltd.] 25.31 g (0.123 mol).
(A) Tridecafluoro-1,1,2,2-tetrahydrooctyltriethoxysilane (FTS-5) [trade name: SIT8175.0, manufactured by Gelest, Inc] 31.33 (0.061 mol).
(B) 67.85 g of ethanol.
(C) Carbonated water (pH = 5.5) 49.79 g.

  The pH of the mixture was 5.4. The log (Mw) of the polysiloxane solution II-1 was 4.2, the initial DC was 71.3, and the DC after 3 months was 81.3. The solid content of the polysiloxane solution II-2 prepared in the same manner as in Example 1 was 7.14.

[Example 3]
A polysiloxane solution III was prepared in the same manner as in Example 1 except that a mixture was prepared using the following, a coating agent 3 was prepared, a charging roller 3 was prepared, and the appearance was evaluated. The results are shown in Table 2.
(A) Glycidoxypropyltriethoxysilane (GPTES) [trade name: KBE-403, manufactured by Shin-Etsu Chemical Co., Ltd.] 19.08 g (0.069 mol) as a hydrolyzable silane compound.
(A) Phenyltriethoxysilane (PhTES) [trade name: KBE-103, manufactured by Shin-Etsu Chemical Co., Ltd.] 65.91 g (0.274 mol).
(A) Hexyltrimethoxysilane (HeTMS) [trade name: KBM-3063, manufactured by Shin-Etsu Chemical Co., Ltd.] 20.17 g (0.098 mol).
(A) Tridecafluoro-1,1,2,2-tetrahydrooctyltriethoxysilane (FTS-5) [trade name: SIT8175.0, manufactured by Gelest, Inc] 24.97 (0.049 mol).
(B) 97.84 g of ethanol.
(C) 52.91 g of carbonated water (pH = 5.5).

The pH of the mixture was 5.8. The log (Mw) of the polysiloxane solution III-1 was 4.3, the initial DC was 67.5, and the DC after 3 months was 79.1. The solid content of the polysiloxane solution III-2 prepared in the same manner as in Example 1 was 7.08.
[Example 4]
A polysiloxane solution IV was prepared in the same manner as in Example 1 except that a mixture was prepared using the following, a coating agent 4 was prepared, a charging roller 4 was prepared, and the appearance was evaluated. The results are shown in Table 2.
(A) Glycidoxypropyltriethoxysilane (GPTS) as a hydrolyzable silane compound [trade name: KBE-403, manufactured by Shin-Etsu Chemical Co., Ltd.] 14.22 g (0.051 mol).
(A) Phenyltriethoxysilane (PhTES) [trade name: KBE-103, manufactured by Shin-Etsu Chemical Co., Ltd.] 49.11 g (0.204 mol).
(A) Hexyltrimethoxysilane (HeTMS) [trade name: KBM-3063, manufactured by Shin-Etsu Chemical Co., Ltd.] 15.03 g (0.073 mol).
(A) Tridecafluoro-1,1,2,2-tetrahydrooctyltriethoxysilane (FTS-5) [trade name: SIT8175.0, manufactured by Gelest, Inc] 18.60 (0.036 mol).
(B) 133.82 g of ethanol.
(C) 49.28 g of carbonated water (pH = 5.5).

The pH of the mixture was 6.1. The log (Mw) of the polysiloxane solution IV-1 was 4.1, the initial DC was 63.4, and the DC after 3 months was 73.6. The solid content of the polysiloxane solution IV-2 prepared in the same manner as in Example 1 was 7.21.
[Example 5]
A polysiloxane solution V was prepared in the same manner as in Example 1 except that a mixture was prepared using the following as carbonated water, a coating agent 5 was prepared, a charging roller 5 was prepared, and the appearance was evaluated. . The results are shown in Table 2.
(C) Carbon dioxide was forcibly dissolved from a liquefied carbon dioxide cylinder under a constant temperature environment to adjust carbonated water having pH = 4.5.

The pH of the mixture was 5.0. The log (Mw) of the polysiloxane solution V-1 was 4.5, the initial DC was 80.3, and the DC after 3 months was 85.0. The solid content of the polysiloxane solution V-2 prepared in the same manner as in Example 1 was 7.25.
[Example 6]
A polysiloxane solution VI was prepared in the same manner as in Example 1 except that a mixture was prepared using the following as carbonated water, a coating agent 6 was prepared, a charging roller 6 was prepared, and the appearance was evaluated. . The results are shown in Table 2.
(C) Water [trade name: purified water (ion-exchanged water), manufactured by Kishida Chemical Co., Ltd.] 1 L was transferred to a polyethylene cup, and the room temperature and humidity environment (23 ± 5 ° C., 60 ± 10% RH) And left open for 24 hours. The pH of the carbonated water at that time was 6.5.

  The pH of the mixture was 6.4. The log (Mw) of the polysiloxane solution VI-1 was 4.0, the initial DC 61.3, and the DC after 3 months was 70.5. The solid content of the polysiloxane solution VI-2 prepared in the same manner as in Example 1 was 6.89.

[Comparative Example 1]
The polysiloxane solution VII was prepared in the same manner as in Example 1 except that the mixture was prepared using hydrochloric acid pH 2.5 instead of carbonated water, the coating agent 7 was prepared, the charging roller 7 was prepared, and the appearance was evaluated. Went. The results are shown in Table 2.

  The pH of the mixture was 1.5. The log (Mw) of the polysiloxane solution VII-1 was 5.2, the initial DC was 93.3, and the DC after 3 months was 95.2. The solid content of the polysiloxane solution VII-2 prepared in the same manner as in Example 1 was 7.15.

[Comparative Example 2]
The polysiloxane solution VIII was prepared in the same manner as in Example 1 except that the mixture was prepared using formic acid pH 4.0 instead of carbonated water, the coating agent 8 was prepared, the charging roller 8 was prepared, and the appearance was evaluated. Went. The results are shown in Table 2.

  The pH of the mixture was 3.0. The log (Mw) of the polysiloxane solution VIII-1 was 4.8, the initial DC was 87.1, and the DC after 3 months was 94.1. The solid content of the polysiloxane solution VIII-2 prepared in the same manner as in Example 1 was 7.16.

[Comparative Example 3]
A polysiloxane solution IX was prepared in the same manner as in Example 1 except that a mixture was prepared using purified water instead of carbonated water, a coating agent 9 was prepared, a charging roller 9 was prepared, and the appearance was evaluated. It was. The results are shown in Table 2.

  The pH of the mixture was 6.5. The log (Mw) of the polysiloxane solution IX-1 was 3.8, the initial DC was 58.1, and the DC after 3 months was 67.2. The solid content of the polysiloxane solution IX-2 prepared in the same manner as in Example 1 was 6.24.

  As described above, according to the present invention, there is almost no residual monomer after synthesis, and white turbidity and phase separation due to excessive reaction are suppressed, and it is uniform and can be stored for a long period of time. A coating agent capable of forming a coating film with reduced s is obtained. Thereby, in the electrophotographic member, it is possible to form a surface layer in which coating unevenness, streaks and the like are suppressed, and a good image can be obtained.

It is a side view which shows an example of the member for electrophotography obtained using the manufacturing method of the member for electrophotography of this invention. It is a figure which shows the relationship between pH of the mixture obtained by the process (1) in the manufacturing method of the coating agent which concerns on this invention , and solid content contained in the polysiloxane solution obtained by a process (2). It is a figure which shows the relationship between the solid content contained in the polysiloxane solution obtained from the process (2) in the manufacturing method of the coating agent which concerns on this invention , and the weight average molecular weight of polysiloxane. It is a schematic block diagram which shows an example of the electrophotographic apparatus to which the member for electrophotography obtained using the manufacturing method of the member for electrophotography of this invention is applied.

Explanation of symbols

103 surface layer 3 charging member 5 developing means 6 transfer roller 7 cleaning means 8 fixing means

Claims (5)

A method for producing an electrophotographic member comprising the following steps (1), (2), (3) and (4) :
(1) a hydrolyzable silane compound containing a compound represented by the following formula (1) (A), the alcohol (B), and pH are mixed carbonated water of 4.5 to 6.5 (C), the Adjusting the pH to 5.0 ≦ pH ≦ 6.4 by the amount of carbonated water (C) to create a mixture;
(2) heating to reflux the mixture, the dehydration condensation reaction of the hydrolyzable silane compound (A), the weight average molecular weight (Mw) containing 4.0 to 4.5 of the polysiloxane in the common logarithm Producing a polysiloxane solution;
(3) adding a photopolymerization initiator (D) to the polysiloxane solution to prepare a coating agent; and
(4) A step of forming a coating layer of the coating agent on the surface of the conductive elastic layer provided on the support and irradiating the coating layer with active energy rays to form a surface layer.

Wherein R ¹¹ and R ¹² independently represent a saturated or unsaturated monovalent hydrocarbon group, Z ¹¹ represents a divalent organic group, and Rc ¹¹ represents an organic group containing an epoxy group. D represents an integer of 0 to 2, e represents an integer of 1 to 3, and d + e = 3.) The method for producing an electrophotographic member according to claim 1 , wherein the carbonated water (C) is carbonated water having a pH of 4.5 to 5.5 . The manufacturing method of the member for electrophotography of Claim 1 or 2 in which the said hydrolysable silane compound (A) contains the compound represented by Formula (2).

(In the formula, R ²¹ and R ^{22 each} independently represents an unsubstituted or substituted alkyl group, Z ²¹ represents a divalent organic group, and Rp ²¹ represents C 1-11 perfluoro. Represents an alkyl group, f represents an integer of 0 to 2, g represents an integer of 1 to 3, and f + g = 3.) The manufacturing method of the member for electrophotography as described in any one of Claim 1 to 3 in which the said hydrolysable silane compound (A) contains the compound represented by Formula (3) :

(In the formula, R ³¹ represents an unsubstituted or phenyl-containing alkyl group or an unsubstituted or alkyl-containing aryl group, R ³² represents a saturated or unsaturated monovalent hydrocarbon group, a represents any integer of 0 to 3, b represents any integer of 1 to 4, and a + b = 4) . Producing how the electrophotographic member according to any one of claims 1 to 4 wherein the photopolymerization initiator (D) contains a cationic polymerization initiator.

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