JP2011112920A - Electrifying member, process cartridge, and electrophotographic device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electrifying member capable of stably controlling a C set image independently of an environment. <P>SOLUTION: The electrifying member has a support and a surface layer where the surface layer contains binder resin, conductive particles, and perfluoropolyether having a specific structure. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a charging member, a process cartridge, and an electrophotographic apparatus.

  When the charging member used for contact charging is brought into contact with the electrophotographic photosensitive member for a long time, deformation (hereinafter referred to as compression set, abbreviated as “C set”) that does not easily recover may occur on the surface. is there. A difference in charging ability is likely to occur between the portion where the C set is generated and the portion where the C set is not generated, which causes an electrophotographic image having density unevenness (hereinafter referred to as “C set image”). A flexible elastic layer made of rubber or foam is known as one of the causes of the C set. The C set generated on the surface layer of the charging member is also a C set regardless of the presence or absence of such an elastic layer. May cause images. In particular, the surface layer has a function of charging the photoconductor by discharging from the surface layer to the photoconductor, so that even if the amount of the C set itself is small, a C set image may be generated. In Patent Document 1, a charging member including an outermost layer containing composite particles in which carbon black is coated on first oxide particles, a second metal oxide, and a binder is effective in reducing C set images. It is described that.

JP 2006-72318 A

  As a result of repeated studies on the charging member described in Patent Document 1, the present inventors are effective in suppressing the C set image, but still have an improvement in the suppression effect of the C set image in a high humidity environment. We gained recognition that there is room for. Accordingly, an object of the present invention is to provide a charging member that can stably suppress C set images under various environments. Another object of the present invention is to provide an electrophotographic apparatus and a process cartridge capable of forming a high-quality electrophotographic image stably in various environments.

（式１中、a及びcは５〜１００の整数であり、ｂは２〜６の整数であり、Ｘは下記式２で示す基である）、

（式２中、Ｒ₁及びＲ_２は各々独立に炭素数１〜８の炭化水素基、Yは*−ＣＨ_２ＣＨ_２−、*−ＯＣＨ_２−、*−ＯＣＨ_２ＣＨ_２−、および*−Ｃ_６Ｈ_４−ＮＲ_１３−ＣＯ−から選ばれる何れかであり、*は、上記式２のケイ素原子への結合部位を示す。ここで、R_１３は水素原子または炭素数１〜８の炭化水素基である。Ｚは炭素数１〜８の炭化水素基、下記化学式（４）で示される基及び下記化学式（５）で示される基から選ばれるいずれかある。）、

（式４中、Ｒ_３〜Ｒ_８は各々独立に炭素数１〜８の炭化水素基であり、ｍは１〜３の整数である）、

（式５中、Ｒ_９〜Ｒ_１２は各々独立に炭素数１〜３の炭化水素基であり、ｎは０〜６の整数である）。 The charging member according to the present invention is a charging member having a support and a surface layer, wherein the surface layer contains a binder resin, conductive particles, and a perfluoropolyether represented by the following formula 1. To:

(In Formula 1, a and c are integers of 5 to 100, b is an integer of 2 to 6, and X is a group represented by Formula 2 below),

(In Formula 2, R ₁ and R ₂ are each independently a hydrocarbon group having 1 to 8 carbon atoms, Y is * —CH ₂ CH ₂ —, * —OCH ₂ —, * —OCH ₂ CH ₂ —, and * —C ₆ H ₄ —NR ₁₃ —CO— is selected, and * represents a bonding site to the silicon atom of the above formula 2. Here, R ₁₃ is a hydrogen atom or a C 1-8 carbon atom. Z is a hydrocarbon group having 1 to 8 carbon atoms, a group represented by the following chemical formula (4) and a group represented by the following chemical formula (5)).

(In Formula 4, R < ₃ > -R < ₈ > is a C1-C8 hydrocarbon group each independently, m is an integer of 1-3),

(In the formula _{5, R} 9 ~R ₁₂ are each independently a hydrocarbon group having 1 to 3 carbon atoms, n is an integer from 0 to 6).

  In addition, a process cartridge according to the present invention includes the above-described charging member and a photosensitive member disposed in contact with the charging member, and is configured to be detachable from the main body of the electrophotographic apparatus. It is characterized by. Furthermore, an electrophotographic apparatus according to the present invention includes the above-described charging member and a photosensitive member disposed in contact with the charging member.

  According to the present invention, C set images can be suppressed even in a high humidity environment.

It is explanatory drawing of the charging member which concerns on this invention. 1 is a cross-sectional view of an electrophotographic apparatus according to the present invention. It is sectional drawing of the process cartridge which concerns on this invention. It is explanatory drawing of the measuring method of the electrical resistance value of the charging roller which concerns on this invention. FIG. 3 is an explanatory diagram of a contact state between a charging roller and an electrophotographic photosensitive member.

[Charging roller]
FIG. 1 is a cross-sectional view of a charging roller as an example of a charging member according to the present invention. The charging roller has a conductive support 1, a conductive elastic layer 2, and a surface layer 3.

上記式１中、a及びcは５〜１００の整数であり、ｂは２〜６の整数であり、Ｘは下記式２で示す基である。

上記式２中、Ｒ_１及びＲ_２は各々独立に炭素数１〜８の炭化水素基を示す。
Yは*−ＣＨ_２ＣＨ_２−、*−ＯＣＨ_２−、*−ＯＣＨ_２ＣＨ_２−、および*−Ｃ_６Ｈ_４−ＮＲ_１３−ＣＯ−から選ばれる何れかであり、*は、上記式２のケイ素原子への結合部位を示す。ここで、Ｒ_１３は水素原子または炭素数１〜８の炭化水素基である。また、Ｚは炭素数１〜８の炭化水素基、下記化学式（４）で示される基及び下記化学式（５）で示される基から選ばれるいずれかある。

上記式４中、Ｒ_３〜Ｒ_８は各々独立に炭素数１〜８の炭化水素基であり、ｍは１〜３の整数である。

上記式５中、Ｒ_９〜Ｒ_１２は各々独立に炭素数１〜３の炭化水素基であり、ｎは０〜６の整数である。 [Surface layer]
The surface layer 3 contains a binder resin, conductive particles, and perfluoropolyether represented by the following formula 1.

In the above formula 1, a and c are integers of 5 to 100, b is an integer of 2 to 6, and X is a group represented by the following formula 2.

Among the above formula 2, _{R 1} and _{R 2} is a hydrocarbon group having 1 to 8 carbon atoms each independently.
Y is any one selected from * —CH ₂ CH ₂ —, * —OCH ₂ —, * —OCH ₂ CH ₂ —, and * —C ₆ H ₄ —NR ₁₃ —CO—, and * represents the above formula 2 shows a bonding site to a silicon atom. Here, R ₁₃ is a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. Z is any one selected from a hydrocarbon group having 1 to 8 carbon atoms, a group represented by the following chemical formula (4), and a group represented by the following chemical formula (5).

In said formula 4, R < ₃ > -R < ₈ > is a C1-C8 hydrocarbon group each independently, and m is an integer of 1-3.

Among the above formula _{5, R} 9 ~R ₁₂ are each independently a hydrocarbon group having 1 to 3 carbon atoms, n is an integer from 0 to 6.

  The perfluoropolyether represented by the above formula 1 has a silyl group at the end of a polymer composed of units derived from perfluoroalkylene oxide. C set is likely to occur in a high temperature and high humidity environment. This is presumably because, under a high temperature and high humidity environment, the penetration of moisture into the surface layer causes the resin in the surface layer to swell and plasticize, and easily deforms due to external forces. The perfluoropolyether according to the present invention has a long-chain perfluoropolyether structure, the surface of the surface layer is hydrophobized by the molecular structure of having a silyl group at the terminal, and moisture in the surface layer is absorbed. Intrusion is thought to be suppressed. Therefore, it is considered that the swelling of the resin in the surface layer and the accompanying plasticization of the surface layer under a high temperature and high humidity environment are suppressed, and as a result, the C set and the C set image are effectively suppressed.

Specific examples of the hydrocarbon group having 1 to 8 carbon atoms represented by R ₁ , R ₂ and Z in the above formula (2), R _{3 to} R _{8 and} R ₁₃ in the above formula (4) are shown below.
・ Linear, branched or cyclic alkyl group (methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, isopentyl group, hexyl group, isohexyl group (2-methylpentyl group) 3-methylpentyl group, 2-ethylbutyl group, cyclohexyl group, heptyl group, isoheptyl group (2-methylhexyl group), 3-methylhexyl group, 2-ethylheptyl group, 2-propylbutyl group, octyl group, isooctyl Group (2-methylheptyl group), 3-methylheptyl group, 4-methylheptyl group, 2-ethylhexyl group, 3-ethylhexyl group, 2-propylpentyl group, 3-propylpentyl group, etc.)
An alkenyl group (for example, ethenyl group, propenyl group, butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, etc.).
-Aryl group (phenyl group, tolyl group, benzyl group, etc.).

Specific examples of the hydrocarbon group having 1 to 3 carbon atoms of R _{9 to} R _{12 in} the above formula (5) include a methyl group, an ethyl group, a propyl group, and an isopropyl group.

  The unit derived from perfluoroalkylene side needs to contain a unit derived from perfluoropropylene oxide. Perfluoropolyether containing units derived from perfluoropropylene oxide has a great effect of suppressing hygroscopicity.

  The number of units derived from perfluoropropylene oxide shown in Formula 1 is 5 to 100. More preferably, it is 15-100. Thereby, generation | occurrence | production of C set image can be suppressed further.

  As a method for introducing a silyl group into the terminal of the perfluoropolyether, synthesis can be performed by reacting a perfluoropolyether having a vinyl group, a hydroxyl group or an acid fluoride group at the terminal with a silane compound in advance. The synthesis method is illustrated below.

  For example, when a perfluoropolyether having a vinyl group at the terminal is used as a starting material, it can be synthesized by subjecting hydrosilane to an addition reaction (hydrosilylation reaction) in the presence of a platinum-based catalyst. For example, when a perfluoropolyether having a hydroxyl group at the terminal is used as the starting material, it can be synthesized by a dealcohol condensation reaction with an alkoxysilane. Alternatively, when a perfluoropolyether having an acid fluoride group at the terminal is used as a starting material, it can be synthesized by reacting with an amino-modified silane in the presence of an acid acceptor such as trimethylamine.

上記式６中、Ｒ_３〜Ｒ_８は各々独立に炭素数１〜８の炭化水素基であり、ｍは１〜３である。

式７中、Ｒ_９〜Ｒ_１２は各々独立に炭素数１〜３の炭化水素基であり、ｎは０〜６である。 In addition, when a polysiloxane group represented by Formula 4 or 5 is introduced, the end of the perfluoropolyether is a vinylsilyl group, and hydrosilane represented by Formula 6 or 7 below is added in the presence of a platinum catalyst (hydrosilylation). Synthesis).

In said formula 6, R < ₃ > -R < ₈ > is a C1-C8 hydrocarbon group each independently, and m is 1-3.

In formula _{7, R} 9 ~R ₁₂ are each independently a hydrocarbon group having 1 to 3 carbon atoms, n represents 0 to 6.

[Conductive particles]
Examples of the conductive particles include metal oxide conductive particles such as carbon black, titanium oxide, tin oxide, and zinc oxide, and metal conductive particles such as aluminum, iron, copper, and silver. Moreover, these electroconductive particle can be used individually or in combination of 2 or more types. Moreover, the composite particle which coat | covered the electroconductive particle on the silica particle can also be used as an electroconductive particle. Below, said composite particle is demonstrated.

  The silica particles are preferably in the range of 5 to 95 parts by mass with respect to 100 parts by mass of the composite particles. The affinity between the silica particles and the perfluoropolyether having a silyl group at the end is good, and the effect of suppressing the hygroscopicity of the composite particles is high. Moreover, the volume resistance value of the composite particles is low, and the resistance adjustment of the surface layer is easy. A more preferable range for the amount of silica particles is 10 to 90 parts by mass.

  The composite particles are produced as follows. For example, the silica particles coated with carbon black are produced by shearing the carbon black and silica particles with a wheel-type kneader. As kneading conditions, the kneading time and the number of wheel rotations are set as appropriate, and kneading is performed until most of the carbon black adheres to the silica particles. In the composite particles of the present invention, the silica particles are preferably coated with the conductive particles through an adhesive. Examples of the adhesive include organosilane compounds formed from alkoxysilanes, and polysiloxanes, modified polysiloxanes, terminal-modified polysiloxanes, or mixtures thereof. The adhesive is attached to the surface of the core particle by a known powder surface treatment method. Known adhesion methods include dry methods and wet methods, and wet methods include aqueous solution methods, organic solvent methods, and spray methods.

The volume resistance value of the composite particles is preferably 10 ⁵ Ω · cm or less. When the volume resistance value of the composite particles is 10 ⁵ Ω · cm or less, the resistance adjustment of the charging member is easy. The volume resistance of the composite particles is a value obtained by putting an appropriate amount of composite particles into a resistance measuring device manufactured by Mitsubishi Chemical Corporation under a 23 ° C./50% RH environment and compressing them by applying a pressure of 10.1 MPa. The sample to be measured. A microammeter (trade name: ADVANTEST R8340A ULTRA HIGH RESISTANCE METER, manufactured by Advantest Co., Ltd.) is connected to this apparatus, a voltage of 200 V is applied, and a current after 30 seconds is measured. And it calculates from the thickness of a sample (composite particle) and an electrode area, and calculates | requires volume resistivity.

[Binder resin]
A known binder resin can be used as the binder resin. As the binder resin, fluorine resin, polyamide resin, acrylic resin, polyurethane resin, silicone resin, butyral resin, styrene-ethylene / butylene-olefin copolymer, olefin-ethylene / butylene-olefin copolymer, and the like can be used.

  These may be used alone, in combination of two or more, or may be a copolymer. In order to make the strength of the surface layer and the hygroscopicity suppressing effect compatible at a high level, the perfluoropolyether polymer is 0.01 parts by mass or more, particularly 0.1-30 parts per 100 parts by mass of the binder resin. It is preferable to contain a mass part. The composite particles are preferably contained in the range of 5 to 70 parts by mass with respect to the binder resin. By setting it as this range, moderate electroconductivity can be obtained, and since discharge is stabilized, the effect of suppressing the C set image is further improved.

  The surface layer may contain organic insulating particles without departing from the spirit of the present invention. Examples of the organic insulating particles include particles made of a polymer compound. Among the polymer compounds, acrylic resin, styrene resin, urethane resin, fluororesin, and silicone resin are preferable from the viewpoint of being relatively high in hardness and not easily deformed when made into particles and being uniformly present in the binder of the charging member. Examples of other insulating particles include titanium oxide, silica, alumina, magnesium oxide, strontium titanate, barium titanate, barium sulfate, calcium carbonate, mica, zeolite, and bentonite. These particles may be used alone or in combination of two or more, and may be subjected to surface treatment, modification, introduction of functional groups or molecular chains, coating, surface treatment, and the like. Absent.

  The surface layer can be formed by a coating method such as electrostatic spray coating or dipping coating. Or it can also form by adhere | attaching or coat | covering the sheet-shaped or tube-shaped layer beforehand formed into a predetermined film thickness. Alternatively, a method of curing and molding the material into a predetermined shape in the mold can also be used.

The optimum electrical resistance value of the surface layer varies depending on the characteristics of the photoreceptor or the type of electrophotographic process, but the volume resistivity is 10 ³ Ω · cm or more and 10 ¹⁴ Ω · cm or less in a 23 ° C./50% RH environment. It is preferable. This is because good charging performance for the photosensitive member can be maintained while suppressing occurrence of leakage. The volume resistivity of the surface layer is measured as follows. First, the surface layer is peeled off from the charging member in a roller state and cut into a strip shape of about 5 mm × 5 mm. A metal is vapor-deposited on both surfaces to produce an electrode and a guard electrode, and a measurement sample is obtained. Alternatively, it is applied on an aluminum sheet to form a surface layer coating film, and a metal is deposited on the coating surface to obtain a measurement sample. A voltage of 200 V is applied to the obtained sample for measurement using a microammeter (ADVANTEST R8340A ULTRA HIGH RESISTANCE METER Co., Ltd., manufactured by Advantest). The current after 30 seconds is measured, and the volume resistivity is obtained by calculating from the film thickness and the electrode area.
The thickness of the surface layer is preferably 1 to 100 μm, particularly 5 to 50 μm.

[Support]
The conductive support has a role of supporting an elastic layer provided thereon and conducting a current necessary for charging. Examples of the material of the conductive support include metals such as iron, aluminum, titanium, copper and nickel, carbon steel containing these metals, alloys such as stainless steel, duralumin, brass and bronze.

[Elastic layer]
The conductive elastic layer is formed, for example, by dispersing a conductive agent in a polymer elastic body. Examples of the polymer elastic body include the following. Examples include synthetic rubbers such as epichlorohydrin rubber, acrylonitrile-butadiene rubber, chloroprene rubber, urethane rubber, and silicone rubber. Alternatively, thermoplastic elastomers such as styrene / butadiene / styrene block copolymers and styrene / ethylene butylene / styrene block copolymers may be used. As the polymer elastic body, epichlorohydrin rubber is particularly preferably used. In the epichlorohydrin rubber, the polymer itself has conductivity in the middle resistance region, and can exhibit good conductivity even if the amount of the conductive agent added is small. Moreover, since the variation in electric resistance depending on the position can be reduced, it is suitably used as a polymer elastic body.

  Examples of the epichlorohydrin rubber include the following. Epichlorohydrin homopolymer, epichlorohydrin-ethylene oxide copolymer, epichlorohydrin-allyl glycidyl ether copolymer and epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer. Of these, epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer is particularly preferably used since it exhibits stable conductivity in a medium resistance region. The epichlorohydrin-ethylene oxide-allyl glycidyl ether terpolymer can control conductivity and workability by arbitrarily adjusting the degree of polymerization and composition ratio.

  As the conductive agent, an ionic conductive agent or an electronic conductive agent can be used. For the purpose of reducing unevenness of the electrical resistivity of the elastic layer, it is preferable to contain an ionic conductive agent. By uniformly dispersing the ionic conductive agent in the polymer elastic body and making the electrical resistance of the conductive elastic body uniform, uniform charging can be obtained even when the charging roller is used with only DC voltage applied. Can do.

  The ionic conductive agent is not particularly limited as long as it is an ionic conductive agent exhibiting ionic conductivity. Examples of the ionic conductive agent include the following. Examples include inorganic ionic substances such as lithium perchlorate, sodium perchlorate, and calcium perchlorate. Examples thereof include quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and tetrabutylammonium perchlorate. Examples thereof include organic acid inorganic salts such as lithium trifluoromethanesulfonate and potassium perfluorobutanesulfonate. These can be used alone or in combination of two or more. Among ionic conductive agents, quaternary ammonium perchlorate is particularly preferably used because of its resistance to environmental changes. The electronic conductive agent is not particularly limited as long as it is conductive particles exhibiting electronic conductivity. For example, carbon black such as furnace black, thermal black, acetylene black and ketjen black, metal oxide conductive particles such as titanium oxide, tin oxide and zinc oxide, metal conductive such as aluminum, iron, copper and silver Particles can be mentioned. Moreover, these electrically conductive agents can be used individually or in combination of 2 or more types.

The amount of the conductive agent is such that the volume resistivity of the conductive elastic body is low temperature and low humidity environment (15 ° C./10% RH), normal temperature and normal humidity environment (23 ° C./50% RH), and high temperature and high humidity environment (30 ° C. / 80% RH), and preferably 1 × 10 ³ to 1 × 10 ⁹ Ω · cm. This is because a charging member exhibiting good charging performance can be obtained. In addition, plasticizers, fillers, vulcanizing agents, vulcanization accelerators, anti-aging agents, scorch preventing agents, dispersants and release agents may be added to the conductive elastic body as necessary. You can also.

  As a method for forming the elastic layer, it is preferable to mix the raw materials of the above-mentioned conductive elastic body with a closed mixer and form the elastic layer by a known method such as extrusion molding, injection molding, or compression molding. The elastic layer may be produced by directly forming a conductive elastic body on the conductive support, or by forming a conductive elastic body previously formed into a tube shape on the conductive support. Also good. Note that the surface may be polished and the shape may be adjusted after the elastic layer is formed.

[Electrophotographic equipment]
FIG. 2 is a schematic configuration diagram of an electrophotographic apparatus according to the present invention. A charging device 5 that charges the photosensitive member 4, a latent image forming device 11 that performs exposure, a developing device 6 that develops the latent image into a toner image, a transfer device 8 that transfers the toner image to a transfer material 7, and a transfer toner on the photosensitive member And a fixing device 9 for fixing the toner image. In FIG. 2, 12 is a pre-charging exposure apparatus, 13 is an elastic regulating blade, 14 is a toner supply roller, 18 is a developing bias application power source, 19 is a charging bias application power source, and 20 is a transfer bias application power source. The photoreceptor 4 is a rotary drum type having a photosensitive layer on a conductive substrate. The photoreceptor is driven to rotate in the direction of the arrow at a predetermined peripheral speed (process speed). The charging device 5 has a contact-type charging roller that is placed in contact with the photosensitive member by being brought into contact with the photosensitive member with a predetermined pressing force. The charging roller is driven rotation that rotates in accordance with the rotation of the photosensitive member, and charges the photosensitive member to a predetermined potential by applying a predetermined DC voltage to the charging roller from a charging power source. As the latent image forming apparatus 11 that forms an electrostatic latent image on the photoreceptor, an exposure apparatus such as a laser beam scanner is used. By performing exposure corresponding to the image information on the uniformly charged photoreceptor, an electrostatic latent image is formed on the photoreceptor. The developing device 6 has a contact-type developing roller disposed close to or in contact with the photoreceptor. The toner electrostatically processed to the same polarity as the charged polarity of the photosensitive member is reversely developed, and the electrostatic latent image is visualized and developed into a toner image. The transfer device 8 has a contact-type transfer roller. The toner image is transferred from the photosensitive member to a transfer material 7 such as plain paper (the transfer material is conveyed by a paper feed system having a conveying member). The cleaning device 10 has a blade-type cleaning member and a collection container, and after transfer, mechanically scrapes and collects transfer residual toner remaining on the photosensitive member. Here, it is also possible to remove the cleaning device by adopting a development simultaneous cleaning system in which the transfer device collects the transfer residual toner. The fixing device 9 is constituted by a heated roll or the like, and fixes the transferred toner image on a transfer material and discharges it outside the apparatus. It is also possible to use the process cartridge shown in FIG. 3 in which the photosensitive member 4, the charging device 5, the developing device 6, the cleaning device 10 and the like are integrated and designed to be detachable from the main body of the electrophotographic image forming apparatus. In FIG. 3, 13 is an elastic regulating blade, 14 is a toner supply roller, and 30 is a toner seal.

  Hereinafter, the present invention will be described in more detail with reference to specific examples.

上記式Ａ中、ａとｃの和の平均が６０、ｂは４である。式Ａで示す化合物は、ＵＳＰ３６６０３１５やＪ．Ｍａｃｒｏｍｏｌ.Ｓｃｉ.Ｃｈｅｍ.Ａ８（3）,４９９（１９７４）に記載された方法に従って、両末端にカルボン酸フルオリド基を有するパーフルオロポリエーテルを用いて合成できる。本製造例においては、具体的には、フッ化セシウムをテトラグライムに溶解させた溶液に、窒素雰囲気下、−３３℃にてシュウ酸フルオリドを加えて１時間攪拌した。その後、−７８℃に冷却し、更にシュウ酸フルオリドとヘキサフルオロプロピレンオキシドを加え、これらを反応させることにより両末端が−ＣＦ_２Ｏ−Ｃｓ基である重合開始剤を得た。この重合開始剤をテトラグライムに加え、窒素雰囲気下、−４０℃に保ちながら、重合促進剤としてのヘキサフルオロプロペンを加え、続いて−３２℃にてヘキサフルオロプロピレンオキシドを加え重合させる。得られた重合体を１５０℃に加熱して、両末端の−ＣＦ_２Ｏ−Ｃｓ基からフッ化セシウムを脱離させ、両末端がカルボン酸フルオリド基を有するパーフルオロポリエーテルを得た。このパーフルオロポリエーテル３０２．１１ｇ（３０ｍｍｏｌ）にジエチルエーテル３００．００ｇを加え、アイスバスにより冷却しながら、窒素雰囲気下、１．０Ｍのメチルマグネシウムヨージドのジエチルエーテル溶液を９０ｍｌ（９０ｍｍｏｌ）滴下し、３０分間加熱還流した。室温に放冷後、８×１０^２Ｐａにて減圧留去してジエチルエーテルを除去し、８５重量％のリン酸を５．００ｇ加え、オイルバスにより１５０℃に保ちながら１時間攪拌した。水で洗浄した後、ろ過して得られた溶液を１００℃、８×１０^２Ｐａにて減圧留去して上記式Ａで示した液状のパーフルオロポリエーテルを得た。次に上記式Ａの液状のパーフルオロポリエーテル２０１．４０ｇ（２０ｍｍｏｌ）にトリフルオロキシレン５０．００ｇを加えた。攪拌しながら、塩化白金酸のイソプロピルアルコール溶液（塩化白金酸２質量％）を０．０５ｇ加えた。オイルバスにより、１００℃に保ちながら、式Ａ−１で示されるシラン化合物５．１６ｇ（６０ｍｍｏｌ）を滴下ロートを用いて滴下し２時間攪拌した。

[Preparation of perfluoropolyether having a silyl group at the end]
(Production Example 1) Perfluoropolyether 1

In the above formula A, the average of the sum of a and c is 60, and b is 4. Compounds represented by Formula A are described in US Pat. According to the method described in Macromol. Sci. Chem. A8 (3), 499 (1974), it can be synthesized using a perfluoropolyether having a carboxylic acid fluoride group at both ends. In this production example, specifically, oxalic fluoride was added to a solution of cesium fluoride dissolved in tetraglyme at −33 ° C. in a nitrogen atmosphere and stirred for 1 hour. Thereafter, the mixture was cooled to −78 ° C., fluoric acid fluoride and hexafluoropropylene oxide were further added, and these were reacted to obtain a polymerization initiator having both ends being —CF ₂ O—Cs groups. This polymerization initiator is added to tetraglyme, and while maintaining at −40 ° C. in a nitrogen atmosphere, hexafluoropropene as a polymerization accelerator is added, and then hexafluoropropylene oxide is added at −32 ° C. for polymerization. The obtained polymer was heated to 150 ° C. to remove cesium fluoride from the —CF ₂ O—Cs groups at both ends, thereby obtaining a perfluoropolyether having both ends having a carboxylic acid fluoride group. Add 300.00 g of diethyl ether to 302.11 g (30 mmol) of this perfluoropolyether, and dropwise add 90 ml (90 mmol) of a 1.0 M methylmagnesium iodide diethyl ether solution under a nitrogen atmosphere while cooling with an ice bath. The mixture was heated to reflux for 30 minutes. After allowing to cool to room temperature, the mixture was distilled off under reduced pressure at 8 × 10 ² Pa to remove diethyl ether, 5.00 g of 85 wt% phosphoric acid was added, and the mixture was stirred for 1 hour while maintaining at 150 ° C. with an oil bath. After washing with water, the solution obtained by filtration was distilled off under reduced pressure at 100 ° C. and 8 × 10 ² Pa to obtain a liquid perfluoropolyether represented by the above formula A. Next, 50.00 g of trifluoroxylene was added to 201.40 g (20 mmol) of the liquid perfluoropolyether of the above formula A. While stirring, 0.05 g of an isopropyl alcohol solution of chloroplatinic acid (chloroplatinic acid 2 mass%) was added. While maintaining at 100 ° C. with an oil bath, 5.16 g (60 mmol) of the silane compound represented by Formula A-1 was dropped using a dropping funnel and stirred for 2 hours.

上記式Ａ−２中、ａとｃの和の平均が６０、ｂは４である。 The mixture was allowed to cool to room temperature, and the solution obtained by filtration was distilled off under reduced pressure at 100 ° C. and 8 × 10 ² Pa to obtain perfluoropolyether 1 represented by the following formula A-2.

In the above formula A-2, the average of the sum of a and c is 60, and b is 4.

上記式Ｂ中、ａとｃの和の平均が６０、ｂは４である。式Ｂで示す化合物は、前記式Ａで示す化合物を用いて作製する。式Ａで示す化合物３０２．１０ｇ（３０ｍｍｏｌ）にテトラヒドロフラン（ＴＨＦ）を３００．００ｇ加え、室温、窒素雰囲気下、１．０ＭのボランのＴＨＦ溶液を１５ｍｌ滴下した。１時間攪拌した後、水５．００ｇ、３．０Ｍの水酸化ナトリウム水を５ｍｌ、３０重量％過酸化水素水を５．００ｇ加えて、さらに１時間攪拌した。水で洗浄した後、ろ過して得られた溶液を１００℃、８×１０^２Ｐａにて減圧留去して式Ｂで示す化合物を得た。得られた式Ｂで示す両末端にヒドロキシル基を有する液状のパーフルオロポリエーテル化合物１５１．５９ｇ（１５ｍｍｏｌ）にトリフルオロキシレン５０．００ｇを加えた。攪拌しながら、下記式Ｂ−１で示されるシラン化合物４．６０ｇ（２０ｍｍｏｌ）、ナトリウムメトキシドを０．００５ｇ加えた。オイルバスにて１５０℃に保ちながら３時間攪拌した。

(Production Example 2) Perfluoropolyether 2

In the above formula B, the average of the sum of a and c is 60, and b is 4. The compound represented by Formula B is prepared using the compound represented by Formula A. 300.2 g of tetrahydrofuran (THF) was added to 302.10 g (30 mmol) of the compound represented by Formula A, and 15 ml of 1.0 M borane in THF was added dropwise at room temperature under a nitrogen atmosphere. After stirring for 1 hour, 5.00 g of water, 5 ml of 3.0 M aqueous sodium hydroxide and 5.00 g of 30 wt% hydrogen peroxide were added, and the mixture was further stirred for 1 hour. After washing with water, the solution obtained by filtration was distilled off under reduced pressure at 100 ° C. and 8 × 10 ² Pa to obtain a compound represented by the formula B. To 151.59 g (15 mmol) of a liquid perfluoropolyether compound having hydroxyl groups at both ends represented by the obtained formula B, 50.00 g of trifluoroxylene was added. While stirring, 4.60 g (20 mmol) of a silane compound represented by the following formula B-1 and 0.005 g of sodium methoxide were added. The mixture was stirred for 3 hours while maintaining at 150 ° C. in an oil bath.

上記式Ｂ−２中、ａとｃの和の平均が６０、ｂは４である。 The perfluoropolyether 2 represented by the following formula B-2 was obtained by distillation under reduced pressure at 100 ° C. and 8 × 10 ² Pa.

In the above formula B-2, the average of the sum of a and c is 60, and b is 4.

上記式Ｃ中、ａとｃの和の平均が６０、ｂは４である。

上記式Ｃ−１中、ａとｃの和の平均が６０、ｂは４である。 (Production Example 3) Perfluoropolyether 3
The compound represented by the formula C is prepared using a perfluoropolyether having both carboxylic acid fluoride groups described in Production Example 1. 300.00 g of diethyl ether was added to 302.11 g (30 mmol) of this perfluoropolyether. This solution is added dropwise to a solution consisting of 1.03 g of lithium aluminum hydride and 50.00 g of diethyl ether and stirred for 1 hour. A compound represented by the formula C by adding 10 g of 10% by weight sodium bicarbonate while cooling in an ice bath, washing with water, and filtering the solution obtained by filtration under reduced pressure at 100 ° C. and 8 × 10 ² Pa. Got. Manufactured in the same manner as in Production Example 2 except that the perfluoropolyether compound represented by Formula B in Production Example 2 was changed to 151.17 g (15 mmol) of the perfluoropolyether compound represented by Formula C, and the following formula C-1 The perfluoropolyether 3 shown in FIG.

In the above formula C, the average of the sum of a and c is 60, and b is 4.

In the formula C-1, the average of the sum of a and c is 60, and b is 4.

上記式Ｄ中、ａとｃの和の平均が６０、ｂは４である。

(Production Example 4) Perfluoropolyether 4
50.00 g of trifluoroxylene was added to 151.62 g (15 mmol) of a liquid perfluoropolyether compound having an acid fluoride group at both ends represented by the following formula D prepared by the method described in Production Example 1. While stirring, at 20.degree. C., 14.46 g (60 mmol) of the amino-modified silane compound represented by Formula D-1 and 5.05 g (50 mmol) of triethylamine were added. It stirred for 2 hours, keeping at 60 degreeC with an oil bath.

In the above formula D, the average of the sum of a and c is 60, and b is 4.

上記式Ｄ−２中、ａとｃの和の平均が６０、ｂは４である。 The perfluoropolyether 4 represented by the following formula D-2 was obtained by depressurizingly distilling at 100 ° C. and 8 × 10 ² Pa.

In the above formula D-2, the average of the sum of a and c is 60, and b is 4.

上記式Ｅ中、ａとｃの和の平均が３０、ｂは２である。）

上記式Ｅ−２中、ａとｃの和の平均が３０、ｂは２である。 (Production Example 5) Perfluoropolyether 5
In Production Example 4, the perfluoropolyether compound represented by the formula D was changed to 75.06 g (15 mmol) of the perfluoropolyether compound represented by the formula E prepared by the same procedure. Further, the amino-modified silane compound represented by the formula D-1 was changed to 13.50 g (60 mmol) of the amino-modified silane compound represented by the formula E-1. Otherwise in the same manner as in Production Example 4, perfluoropolyether 5 represented by the following formula E-2 was obtained.

In the above formula E, the average of the sum of a and c is 30, and b is 2. )

In the above formula E-2, the average of the sum of a and c is 30, and b is 2.

上記式Ｆ中、ａとｃの和の平均が３０、ｂは４である。

上記式Ｆ−２中、ａとｃの和の平均が３０、ｂは４である。 (Production Example 6) Perfluoropolyether 6
In Production Example 1, the perfluoropolyether compound represented by the formula A was changed to 103.48 g (20 mmol) of the perfluoropolyether compound represented by the following formula F prepared by the same procedure. In addition, the silane compound represented by Formula A-1 was changed to 8.88 grams (60 mmol) of the silane compound represented by Formula F-1. Other than that was carried out similarly to manufacture example 1, and obtained the perfluoropolyether 6 shown to the following formula F-2.

In the above formula F, the average of the sum of a and c is 30, and b is 4.

In the formula F-2, the average of the sum of a and c is 30, and b is 4.

上記式Ｇ中、ａとｃの和の平均が３０、ｂは６である。

上記式Ｇ−２中、ａとｃの和の平均が３０、ｂは６である。 (Production Example 7) Perfluoropolyether 7
In Production Example 2, the perfluoropolyether compound represented by the formula B was changed to 81.03 g (15 mmol) of the perfluoropolyether compound represented by the formula G prepared by the same procedure. Moreover, the silane compound shown by Formula B-1 was changed into 12.12 g (20 mmol) of the silane compound shown by Formula G-1. Otherwise in the same manner as in Production Example 2, a perfluoropolyether 7 represented by the formula G-2 was obtained.

In the above formula G, the average of the sum of a and c is 30 and b is 6.

In the above formula G-2, the average of the sum of a and c is 30 and b is 6.

上記式Ｈ中、ａとｃの和の平均が３０、ｂは２である。 (Production Example 8) Perfluoropolyether 8

In the above formula H, the average of the sum of a and c is 30, and b is 2.

To 75.06 g (15 mmol) of a perfluoropolyether compound having acid fluoride groups at both ends represented by the above formula H, 50.00 g of trifluoroxylene was added. While stirring, at 20.degree. C., 11.58 g (60 mmol) of the amino-modified silane compound represented by the formula H-1 and 5.05 g (50 mmol) of triethylamine were added. It stirred for 2 hours, keeping at 60 degreeC with an oil bath.

The mixture was allowed to cool to room temperature, and the solution obtained by filtration was distilled off under reduced pressure at 100 ° C. and 8 × 10 ² Pa. After adding 50.00 g of trifluoroxylene and heating to 100 ° C. in an oil bath, 0.05 g of isopropyl alcohol solution of chloroplatinic acid (2% by mass of chloroplatinic acid) was added. While maintaining the temperature at 100 ° C. in an oil bath, 6.24 g (30 mmol) of the silane compound represented by the formula H-2 was dropped using a dropping funnel and stirred for 2 hours.

After allowing the mixture to cool to room temperature, the solution obtained by filtration is distilled off under reduced pressure at 100 ° C. and 8 × 10 ² Pa, and X in Formula 1 has a structure represented by Formula H-3 below. In addition, a perfluoropolyether 8 in which the average of the sum of a and c was 30 and b was 2 was obtained.
Formula H-3
HSi (CH ₃ ) _2- [OSi (CH ₃ ) ₂ ] ₁ -OSi (CH ₃ ) ₂ -CH ₂ CH ₂ -Si (CH ₃ ) ₂ -C ₆ H ₄ -N (CH ₃ ) CO-

式Ｉ−１
HSi(CH₃)₂-[OSi(CH₃)₂]₂-OSi(CH₃)₂-CH₂CH₂-Si(CH₃)₂-C₆H₄-N(CH₃)CO- (Production Example 9) Perfluoropolyether 9
In Production Example 8, the silane compound represented by Formula H-2 was changed to 8.46 g (30 mmol) of the silane compound represented by Formula I. Otherwise, in the same manner as in Production Example 8, X in formula 1 has a structure represented by formula I-1 below, and a perfluoropolyether 9 in which the average of the sum of a and c is 30 and b is 2 is obtained. It was.

Formula I-1
HSi (CH ₃ ) _2- [OSi (CH ₃ ) ₂ ] ₂ -OSi (CH ₃ ) ₂ -CH ₂ CH ₂ -Si (CH ₃ ) ₂ -C ₆ H ₄ -N (CH ₃ ) CO-

式Ｊ−１
HSi(CH₃)₂-[OSi(CH₃)₂]₃-OSi(CH₃)₂-CH₂CH₂-Si(CH₃)₂-C₆H₄-N(CH₃)CO- (Production Example 10) Perfluoropolyether 10
In Production Example 8, the silane compound represented by Formula H-2 was changed to 10.68 g (30 mmol) of the silane compound represented by Formula J. Otherwise, in the same manner as in Production Example 8, X in formula 1 has a structure represented by the following formula J-1, and the average of the sum of a and c is 30, and b is 2. Got.

Formula J-1
HSi (CH ₃ ) _2- [OSi (CH ₃ ) ₂ ] ₃ -OSi (CH ₃ ) ₂ -CH ₂ CH ₂ -Si (CH ₃ ) ₂ -C ₆ H ₄ -N (CH ₃ ) CO-

式Ｋ−１
HSi(C₃H₇)₂-[OSi(C₃H₇)₂]₁-OSi(C₃H₇)₂-CH₂CH₂-Si(CH₃)₂-C₆H₄-N(CH₃)CO- (Production Example 11) Perfluoropolyether 11
In Production Example 8, the silane compound represented by Formula H-2 was changed to 11.28 g (30 mmol) of the silane compound represented by Formula K. Otherwise, in the same manner as in Production Example 8, X in formula 1 has a structure represented by the following formula K-1, and the average of the sum of a and c is 30, and b is 2. Got.

Formula K-1
HSi (C ₃ H ₇ ) _2- [OSi (C ₃ H ₇ ) ₂ ] ₁ -OSi (C ₃ H ₇ ) ₂ -CH ₂ CH ₂ -Si (CH ₃ ) ₂ -C ₆ H ₄ -N (CH ₃ ) CO-

上記式Ｌ−１中、ａとｃの和の平均が３０、ｂは２である。 Production Example 12 Perfluoropolyether 12
In Production Example 8, the silane compound represented by Formula H-2 was changed to 3.600 g (30 mmol) of the silane compound represented by Formula L. Other than that was carried out similarly to manufacture example 8, and obtained the perfluoropolyether 12 shown to following formula L-1.

In the formula L-1, the average of the sum of a and c is 30, and b is 2.

上記式Ｍ−１中、ａとｃの和の平均が３０、ｂは２である。 (Production Example 13) Perfluoropolyether 13
In Production Example 8, the silane compound represented by Formula H-2 was changed to 5.82 g (30 mmol) of the silane compound represented by Formula M. Other than that was carried out similarly to manufacture example 8, and obtained the perfluoropolyether 13 shown to following formula M-1.

In the above formula M-1, the average of the sum of a and c is 30, and b is 2.

上記式Ｎ−１中、ａとｃの和の平均が３０、ｂは２である。 Production Example 14 Perfluoropolyether 14
In Production Example 8, the silane compound represented by Formula H-2 was changed to 8.04 g (30 mmol) of the silane compound represented by Formula N. Otherwise in the same manner as in Production Example 8, a perfluoropolyether 14 represented by the following formula N-1 was obtained.

In the above formula N-1, the sum of a and c is 30 and b is 2.

上記式Ｏ−１中、ａとｃの和の平均が３０、ｂは２である。 Production Example 15 Perfluoropolyether 15
In Production Example 8, the silane compound represented by Formula H-2 was changed to 16.92 g (30 mmol) of the silane compound represented by Formula O. Otherwise in the same manner as in Production Example 8, a perfluoropolyether 15 represented by the following formula O-1 was obtained.

In the formula O-1, the average of the sum of a and c is 30, and b is 2.

上記式Ｐ中、ａとｃの和の平均が１０、ｂは２である。

上記式Ｐ−１中、ａとｃの和の平均が３０、ｂは２である。 Production Example 16 Perfluoropolyether 16
In Production Example 2, the perfluoropolyether compound represented by Formula B was changed to 31.35 g (15 mmol) of the perfluoropolyether compound represented by Formula P prepared by the same procedure. Otherwise in the same manner as in Production Example 2, a perfluoropolyether 16 represented by the following formula P-1 was obtained.

In the above formula P, the average of the sum of a and c is 10, and b is 2.

In the above formula P-1, the average of the sum of a and c is 30, and b is 2.

上記式Ｑ中、ａとｃの和の平均が１０、ｂは２である。

上記式Ｑ−２中、ａとｃの和の平均が１０、ｂは２である。 Production Example 17 Perfluoropolyether 17
In Production Example 1, the perfluoropolyether compound represented by the formula A was changed to 29.37 g (20 mmol) of the perfluoropolyether compound represented by the formula Q prepared by the same procedure. Further, the silane compound represented by Formula A-1 was changed to 11.16 g (60 mmol) of the silane compound represented by Formula Q-1. Other than that was carried out similarly to manufacture example 1, and obtained the perfluoropolyether 17 shown to following formula Q-2.

In the above formula Q, the average of the sum of a and c is 10, and b is 2.

In the above formula Q-2, the average of the sum of a and c is 10, and b is 2.

上記式Ｒ中、ａとｃの和の平均が１０、ｂは２である。

上記式Ｒ−２中、ａとｃの和の平均が１０、ｂは２である。 Production Example 18 Perfluoropolyether 18
In Production Example 4, the perfluoropolyether compound represented by the formula D was changed to 31.62 g (15 mmol) of the perfluoropolyether compound represented by the formula R prepared by the same procedure. Further, the amino-modified silane compound represented by the formula D-1 was changed to 11.58 g (60 mmol) of the amino-modified silane compound represented by the formula R-1. Otherwise in the same manner as in Production Example 4, perfluoropolyether 18 represented by the following formula R-2 was obtained.

In the above formula R, the average of the sum of a and c is 10, and b is 2.

In the above formula R-2, the average of the sum of a and c is 10, and b is 2.

上記式Ｓ中、ａとｃの和の平均が１００、ｂは２である。

上記式Ｓ−２中、ａとｃの和の平均が１００、ｂは２である。 Production Example 19 Perfluoropolyether 19
In Production Example 4, the perfluoropolyether compound represented by the formula D was changed to 245.94 g (15 mmol) of the perfluoropolyether compound represented by the formula S prepared by the same procedure. Further, the amino-modified silane compound represented by the formula D-1 was changed to 16.62 g (60 mmol) of the amino-modified silane compound represented by the formula S-1. Other than that was carried out similarly to manufacture example 4, and obtained the perfluoropolyether 19 shown to following formula S-2.

In the above formula S, the average of the sum of a and c is 100, and b is 2.

In the above formula S-2, the average of the sum of a and c is 100, and b is 2.

上記式Ｔ−１中、ａとｃの和の平均が１００、ｂは２である。 Production Example 20 Perfluoropolyether 20
The amino-modified silane compound represented by Formula S-1 in Production Example 19 was changed to 9.90 g (60 mmol) of the amino-modified silane compound represented by Formula T. Otherwise in the same manner as in Production Example 19, a perfluoropolyether 20 represented by the following formula T-1 was obtained.

In the above formula T-1, the average of the sum of a and c is 100, and b is 2.

上記式Ｕ中、ａとｃの和の平均が１００、ｂは２である。

上記式Ｕ−１中、ａとｃの和の平均が１００、ｂは２である。 Production Example 21 Perfluoropolyether 21
The perfluoropolyether compound represented by Formula Q in Production Example 17 was changed to 329.40 g (20 mmol) of the perfluoropolyether compound represented by Formula U prepared in the same procedure. Other than that was carried out similarly to manufacture example 17, and obtained the perfluoropolyether 21 shown to the following formula U-1.

In the above formula U, the average of the sum of a and c is 100, and b is 2.

In the above formula U-1, the sum of a and c is 100 and b is 2.

上記式Ｖ中、ａとｃの和の平均が２００、ｂは４である。

（式中、ａとｃの和の平均が２００である。ｂは４である。） Production Example 22 Perfluoropolyether 22
In Production Example 1, the perfluoropolyether compound represented by Formula A was changed to 103.48 g (20 mmol) of the perfluoropolyether compound represented by Formula V prepared in the same procedure. Further, the silane compound represented by Formula A-1 was changed to 8.88 g (60 mmol) of the silane compound represented by Formula V-1. Other than that was carried out similarly to manufacture example 1, and obtained the perfluoropolyether 22 shown to following formula V-2.

In the above formula V, the average of the sum of a and c is 200, and b is 4.

(In the formula, the average of the sum of a and c is 200. b is 4.)

上記式Ｗ中、ａとｃの和の平均が２００、ｂは４である。

上記式Ｗ−２中、ａとｃの和の平均が２００、ｂは４である。 Production Example 23 Perfluoropolyether 23
In Production Example 4, the perfluoropolyether compound represented by Formula D was changed to 161.98 g (5 mmol) of the perfluoropolyether compound represented by Formula W prepared in the same procedure. Further, the amino-modified silane compound represented by the formula D-1 was changed to 3.90 g (20 mmol) of the amino-modified silane compound represented by the formula W-1. Other than that was carried out similarly to manufacture example 4, and obtained the perfluoropolyether 23 shown to following formula W-2.

In the above formula W, the average of the sum of a and c is 200, and b is 4.

In the above formula W-2, the average of the sum of a and c is 200, and b is 4.

上記式Ｘ中、ａとｃの和の平均が２００、ｂは４である。

上記式Ｘ−１中、ａとｃの和の平均が２００、ｂは４である。 Production Example 24 Perfluoropolyether 24
In Production Example 2, the perfluoropolyether compound represented by formula B was changed to 162.53 g (5 mmol) of the perfluoropolyether compound represented by formula X prepared in the same procedure. Other than that was carried out similarly to manufacture example 2, and obtained the perfluoropolyether 24 shown to following formula X-1.

In the above formula X, the average of the sum of a and c is 200, and b is 4.

In the above formula X-1, the average of the sum of a and c is 200, and b is 4.

(Production Example 25) Composite conductive fine particles 1
To 5.0 kg of silica particles (average particle diameter 15 nm, volume resistivity 2.0 × 10 ¹² Ω · cm), 100 g of methyl hydrogen polysiloxane was added while operating the edge runner, and 588 N / cm (60 kg / cm ) Was mixed and stirred for 30 minutes. The stirring speed at this time was 22 rpm. Into this, 5.0 kg of carbon black particles (particle diameter 18 nm, volume resistivity 2.1 × 10 ⁻¹ Ω · cm, pH 3.5) was added over 10 minutes while operating the edge runner, and 588 N The mixture was stirred for 60 minutes with a linear load of 50 cm / cm (60 kg / cm). After carbon black was adhered to the surface of the silica particles coated with methyl hydrogen polysiloxane in this way, drying was performed at 80 ° C. for 60 minutes using a dryer, and composite conductive fine particles 1 were obtained. The stirring speed at this time was 22 rpm. The obtained composite conductive fine particles 1 had an average particle diameter of 15 nm and a volume resistivity of 2.1 × 10 ² Ω · cm.

(Production Example 26) Composite conductive fine particle 2
Production was conducted in the same manner as in Production Example 25 except that the amount of carbon black particles added in Production Example 25 was 2.5 kg. The obtained composite conductive fine particles 2 had an average particle diameter of 15 nm and a volume resistivity of 3.5 × 10 ² Ω · cm.

(Production Example 27) Composite conductive fine particles 3
Production was conducted in the same manner as in Production Example 25 except that the amount of carbon black particles added in Production Example 25 was 10.0 kg. The obtained composite conductive fine particles 3 had an average particle diameter of 16 nm and a volume resistivity of 1.1 × 10 ² Ω · cm.

(Production Example 28) Composite conductive fine particles 4
Production was carried out in the same manner as in Production Example 25 except that the addition amount of silica particles in Production Example 25 was 1.0 kg and the addition amount of carbon black particles was 9.0 kg. The obtained composite conductive fine particles 4 had an average particle diameter of 18 nm and a volume resistivity of 1.5 × 10 ¹ Ω · cm.

(Production Example 29) Conductive Elastic Roller The raw materials shown in Table 1-1 below were kneaded for 10 minutes with a pressure kneader whose temperature was adjusted to 100 ° C. Furthermore, 1 part by mass of tetramethylthiuram monosulfide as a vulcanization accelerator and 2 parts by mass of sulfur as a vulcanizing agent were added and kneaded for 10 minutes with an open roll adjusted to a temperature of 25 ° C. to prepare a raw material compound. .

  A conductive support was prepared by nickel-plating the surface of a steel cylindrical shaft having a diameter of 6 mm and a length of 252.5 mm. A thermosetting adhesive (carbon content 2% by mass, methyl isobutyl ketone content 50% by mass) is applied to a 230 mm wide region excluding both ends of the support, and heated at a temperature of 80 ° C. for 30 minutes. The adhesive layer was cured by heating at a temperature of 160 ° C. for 30 minutes.

On the other hand, the obtained raw material compound was rolled around the conductive support under the condition that the screw rotation speed was 15 rpm, the cylinder temperature and the head temperature were adjusted to 70 ° C. by a rubber extruder (inner diameter 50 mm, L / D 20). It shape | molded so that it might become. The roller-shaped molding was vulcanized and the adhesive was cured in an electric oven at 160 ° C. for 30 minutes. Next, both end portions of the rubber portion were removed, and the longitudinal width of the elastic layer portion was set to 232 mm. Thereafter, the rubber portion is polished by a plunge polishing machine (whetstone GC120, wheel diameter φ300 mm, wheel rotation speed 2500 rpm, workpiece rotation speed 333 rpm), and a crown-shaped conductive elasticity having an end diameter of 8.3 mm and a center diameter of 8.5 mm. Got Laura. The conductive elastic roller had a roller resistance of 1 × 10 ⁶ Ω, a surface roughness of Rzjis 1994 of 4.5 μm, and a hardness of 80 degrees (Asker C).

Example 1
[Preparation of Surface Layer Coating] Surface Layer Coating A methyl isobutyl ketone was added to a caprolactone-modified acrylic polyol solution (hydroxyl value 80) to adjust the solid content to 14% by mass. The components shown in Table 1-2 below were added to 714.3 parts by mass of this solution (100 parts by mass of acrylic polyol solid content) to prepare a mixed solution.

(* 1) A 7: 3 mixture of each butanone oxime block of hexamethylene diisocyanate (HDI) and isophorone diisocyanate (IPDI).
(* 2) A trifluoroxylene solution in which 50% of perfluoropolyether 1 is dissolved is prepared and added so that perfluoropolyether 1 is in the above-mentioned parts by mass with respect to 100 parts by mass of acrylic polyol solid content. .

  In the above mixed solution, the blocked isocyanate mixture (* 1) was such that the amount of isocyanate was “NCO / OH = 1.0”.

  200 g of the above mixed solution was placed in a glass bottle with an internal volume of 450 mL together with 200 g of glass beads having an average particle diameter of 0.8 mm as a medium, and dispersed for 18 hours using a paint shaker disperser. After the dispersion, 2.35 g of polymethyl methacrylate resin particles having an average particle diameter of 10 μm were added. Thereafter, the mixture was dispersed for 1 hour, and the glass beads were removed to obtain a coating material for forming the surface layer.

[Production of charging roller]
Using the coating material, dipping coating was applied to the conductive elastic roller produced in Production Example 29. The dipping coating was performed as follows. That is, the dipping coating lowering speed is 30 mm / s, the dipping time is 9 seconds, the dipping coating lifting speed is the initial speed of 20 mm / s, and the final speed is 2 mm / s. It was. Then, air-dry at room temperature for 30 minutes or more, then dry in a hot air circulating dryer at a temperature of 80 ° C. for 1 hour, further at a temperature of 160 ° C. for 1 hour to form a surface layer on the conductive elastic layer, A charging roller was obtained.

[Measurement of resistance of charging roller]
The electrical resistance of the charging roller was measured using the electrical resistance value measuring device shown in FIG. First, the charging roller is brought into contact with the cylindrical metal 32 (diameter 30 mm) by the bearing 33 so as to be parallel to the cylindrical metal 32 (FIG. 4A). In FIG. 4A, 1 is a conductive support, and 5 is a charging roller. Next, the charging roller is driven to rotate in accordance with a cylindrical metal 32 that is driven to rotate at a peripheral speed of 45 mm / s by a motor (not shown). During the driven rotation, as shown in FIG. 4B, a DC voltage of −200 V is applied from the stabilized power source 34, and the current value flowing through the charging roller is measured by the ammeter 35. The resistance of the charging roller was calculated from the applied voltage and current value. The charging roller was allowed to stand for 24 hours or more in an N / N (normal temperature and normal humidity: 23 ° C./55% RH) environment, and the electrical resistance value was measured. The electric resistance value of the charging roller was 6.5 × 10 ⁵ Ω.

[C set image evaluation test]
As an electrophotographic apparatus having the configuration shown in FIG. 2, a Canon color laser printer (color laser jet 3800) was modified to a recording medium output speed of 200 mm / s (A4 vertical output). The resolution of the image is 600 dpi, and the primary charging output is a DC voltage of −1100V. As the process cartridge having the configuration shown in FIG. 3, the black process cartridge for the printer was used. A charging roller to be evaluated was attached to the process cartridge. Then, as shown in FIG. 5, the charging roller 5 was brought into contact with the photosensitive member 4 with a pressing force of a spring of 4.9 N at one end and a total of 9.8 N at both ends. In FIG. 5, 1 indicates a conductive support. The process cartridge was placed in a 40 ° C., 95% RH environment for 1 month. Next, the process cartridge was placed in a 23 ° C./55% RH environment for 6 hours, and then mounted on the electrophotographic apparatus, and an image was output in the same environment. The C set image was evaluated for the output image. The evaluation results are shown in Table 2. Here, the evaluation criteria are as follows.
Rank 1: No C set image is generated.
Rank 2: Minor streaks are observed in the image.
Rank 3: A streak generated at the pitch of the charging roller is recognized in the image.
Rank 4: Many streaks are recognized in the image.

[Measurement of C set amount]
After the image output, the charging roller was removed from the process cartridge, and the radius of the charging roller in the C set portion and the non-C set portion was measured. The difference between the radius of the non-C set portion and the radius of the C set portion is the C set amount. For the measurement, a fully automatic roller measuring device manufactured by Tokyo Koden Kogyo Co., Ltd. was used. The charging roller was rotated by 1 ° at each of the charging roller longitudinal center portion and three positions 90 mm on the left and right sides from the center portion, and the radii at positions corresponding to the C set portion and the non-C set portion were measured. Next, the difference between the maximum value of the radius of the non-C set portion and the minimum value of the radius of the C set portion was calculated. The value with the largest radius difference among the three locations was defined as the C set amount of the present invention. In the charging roller of the present invention, the C set image was rank 1 where no occurrence occurred, and a good image was obtained.

(Examples 2 to 4)
A charging roller was produced in the same manner as in Example 1 except that the type and addition amount of the composite particles were changed as shown in Table 2-1. The mass part of Table 2-1 is a mass part with respect to 100 mass parts of said acrylic polyol solid content. The manufactured charging roller was evaluated in the same manner as in Example 1.

(Examples 5 to 8)
The perfluoropolyether 1 in Example 1 was changed to the perfluoropolyether 18, and the addition amount was changed to 0.1 mass part, 10 mass parts, 30 mass parts or 40 mass parts. Except for these, a charging roller was prepared in the same manner as in Example 1 and evaluated in the same manner as in Example 1.

(Examples 9 to 11)
A charging roller was produced in the same manner as in Example 1 except that the perfluoropolyether 1 in Example 1 was changed to perfluoropolyether 2, 3 or 4 and evaluated in the same manner as in Example 1.

（＊１）は、実施例１に同じ。また、上記の混合溶液において、ブロックイソシアネート混合物（＊１）は、イソシアネート量としては「ＮＣＯ／ＯＨ＝１．０」となる量であった。 (Example 12)
Methyl isobutyl ketone was added to the caprolactone-modified acrylic polyol solution (hydroxyl value 80) to adjust the solid content to 15% by mass. The material of the following Table 1-3 was added with respect to 666.6 mass parts (100 mass parts of acryl polyol solid content) of this solution, and the mixed solution was prepared.

(* 1) is the same as in Example 1. Further, in the above mixed solution, the blocked isocyanate mixture (* 1) was such that the amount of isocyanate was “NCO / OH = 1.0”.

  200 g of the above mixed solution was placed in a glass bottle with an internal volume of 450 mL together with 200 g of glass beads having an average particle diameter of 0.8 mm as a medium, and dispersed for 24 hours using a paint shaker disperser. After the dispersion, 2.55 g of polymethyl methacrylate resin particles having an average particle diameter of 10 μm was added. Thereafter, the mixture was dispersed for 1 hour, and the glass beads were removed to obtain a coating material for forming the surface layer. A charging roller was prepared in the same manner as in Example 1 except that this paint was used, and evaluated in the same manner as in Example 1.

(Examples 13 to 22)
A charging roller was prepared in the same manner as in Example 12 except that the perfluoropolyether 5 in Example 12 was changed to perfluoropolyethers 6 to 15, and evaluated in the same manner as in Example 1.

(Example 23)
Methyl isobutyl ketone was added to the caprolactone-modified acrylic polyol solution (hydroxyl value 80) to adjust the solid content to 16% by mass. The following Table 1-4 components were added to 625.0 parts by mass of this solution (100 parts by mass of acrylic polyol solid content) to prepare a mixed solution.

(* 1) is the same as in Example 1. Further, in the above mixed solution, the blocked isocyanate mixture was such that the amount of isocyanate was “NCO / OH = 1.0”.

  200 g of the above mixed solution was placed in a glass bottle with an internal volume of 450 mL together with 200 g of glass beads having an average particle diameter of 0.8 mm as a medium, and dispersed for 24 hours using a paint shaker disperser. After the dispersion, 3.20 g of polymethyl methacrylate resin particles having an average particle diameter of 10 μm were added. Thereafter, dispersion was performed for 1 hour, and the glass beads were removed to obtain a coating material for forming the surface layer. A charging roller was prepared in the same manner as in Example 1 except that this paint was used, and evaluated in the same manner as in Example 1.

(Examples 24-28)
A charging roller was produced in the same manner as in Example 23 except that the perfluoropolyether 16 in Example 23 was changed to perfluoropolyethers 17 to 21 and evaluated in the same manner as in Example 1.

(Example 29)
Methyl isobutyl ketone was added to the fluorine-modified polyol solution (hydroxyl value 32), and the solid content was adjusted to 20% by mass. Components shown in Table 1-5 below were added to 500.0 parts by mass of this solution (100 parts by mass of fluorine-modified polyol solid content) to prepare a mixed solution.

(* 1) is the same as in Example 1. (* 3) prepares a trifluoroxylene solution in which 50% of perfluoropolyether 22 is dissolved, and is added so that the perfluoropolyether 22 becomes the above-mentioned parts by mass with respect to 100 parts by mass of the fluorine-modified polyol solid content. What you did.

  200 g of the above mixed solution was placed in a glass bottle having an inner volume of 450 mL together with 200 g of glass beads having an average particle diameter of 0.8 mm as a medium, and dispersed for 12 hours using a paint shaker disperser. After the dispersion, 3.20 g of polymethyl methacrylate resin particles having an average particle diameter of 10 μm were added. Thereafter, the mixture was dispersed for 1 hour, and the glass beads were removed to obtain a coating material for forming the surface layer. A charging roller was prepared in the same manner as in Example 1 except that this paint was used, and evaluated in the same manner as in Example 1.

(Examples 30 and 31)
A charging roller was produced in the same manner as in Example 29 except that the perfluoropolyether 22 in Example 29 was changed to perfluoropolyether 23 or 24, and evaluated in the same manner as in Example 1.

(Comparative Example 1)
A charging roller was produced in the same manner as in Example 12 except that perfluoropolyether was not added. The manufactured charging roller was evaluated in the same manner as in Example 1.

(Comparative Example 2)
Methyl isobutyl ketone was added to the fluorine-modified polyol solution (hydroxyl value 32), and the solid content was adjusted to 21% by mass. The components shown in Table 1-6 below were added to 476.1 parts by mass of this solution (100 parts by mass of fluorine-modified polyol solid content) to prepare a mixed solution.

(* 1) is the same as in Example 1. Further, in the above mixed solution, the blocked isocyanate mixture was such that the amount of isocyanate was “NCO / OH = 1.0”.

  200 g of the above mixed solution was placed in a glass bottle having an inner volume of 450 mL together with 200 g of glass beads having an average particle diameter of 0.8 mm as a medium, and dispersed for 12 hours using a paint shaker disperser. After the dispersion, 2.00 g of polymethyl methacrylate resin particles having an average particle size of 10 μm was added. Thereafter, the mixture was dispersed for 1 hour, and the glass beads were removed to obtain a coating material for forming the surface layer. A charging roller was prepared in the same manner as in Example 1 except that this paint was used, and evaluated in the same manner as in Example 1.

（アウシモント社 ＦＯＭＢＬＩＮ Ｚ ＤＯＬ ｐ／ｑ＝１） (Comparative Example 3)
A charging roller was produced in the same manner as in Example 12 except that the perfluoropolyether 5 in Example 12 was changed to the perfluoropolyether 25 represented by Formula Y, and evaluated in the same manner as in Example 1.

(AUSHIMONT FOBBLIN Z DOL p / q = 1)

(Comparative Example 4)
A charging roller was produced in the same manner as in Example 12 except that the perfluoropolyether 5 in Example 12 was changed to perfluorooctylethyltrimethoxysilane represented by Formula Z, and evaluated in the same manner as in Example 1.

（＊１）は実施例１に同じ。また、上記混合溶液において、ブロックイソシアネート混合物は、イソシアネート量としては「ＮＣＯ／ＯＨ＝１．０」となる量であった。 (Comparative Example 5)
Methyl isobutyl ketone was added to the caprolactone-modified acrylic polyol solution (hydroxyl value 80) to adjust the solid content to 15% by mass. The components shown in Table 1-7 below were added to 666.6 parts by mass of this solution (100 parts by mass of acrylic polyol solid content) to prepare a mixed solution.

(* 1) is the same as in Example 1. Further, in the above mixed solution, the blocked isocyanate mixture was such that the amount of isocyanate was “NCO / OH = 1.0”.

  200 g of the above mixed solution was placed in a glass bottle with an internal volume of 450 mL together with 200 g of glass beads having an average particle diameter of 0.8 mm as a medium, and dispersed for 24 hours using a paint shaker disperser. After dispersion, 2.54 g of polymethyl methacrylate resin particles having an average particle diameter of 10 μm was added. Thereafter, the mixture was dispersed for 1 hour, and the glass beads were removed to obtain a coating material for forming the surface layer. A charging roller was prepared in the same manner as in Example 1 except that this paint was used, and evaluated in the same manner as in Example 1.

The evaluation results of the above examples and comparative examples are shown in Table 2 below.

DESCRIPTION OF SYMBOLS 1 Conductive support body 2 Elastic layer 3 Surface layer 4 Photoconductor

Claims (3)

A charging member having a support and a surface layer, wherein the surface layer contains a binder resin, conductive particles and a perfluoropolyether represented by the following formula 1:

(In Formula 1, a and c are integers of 5 to 100, b is an integer of 2 to 6, and X is a group represented by Formula 2 below),

(In Formula 2, R ₁ and R ₂ are each independently a hydrocarbon group having 1 to 8 carbon atoms, Y is * —CH ₂ CH ₂ —, * —OCH ₂ —, * —OCH ₂ CH ₂ —, and * —C ₆ H ₄ —NR ₁₃ —CO— is selected, and * represents a bonding site to the silicon atom of Formula 2. R ₁₃ represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. Z is any one selected from a hydrocarbon group having 1 to 8 carbon atoms, a group represented by the following chemical formula (4), and a group represented by the following chemical formula (5).

(In Formula 4, R < ₃ > -R < ₈ > is a C1-C8 hydrocarbon group each independently, m is an integer of 1-3),

(In the formula _{5, R} 9 ~R ₁₂ are each independently a hydrocarbon group having 1 to 3 carbon atoms, n is an integer from 0 to 6).   A process cartridge comprising: the charging member according to claim 1; and a photosensitive member disposed in contact with the charging member, wherein the process cartridge is detachable from a main body of the electrophotographic apparatus. .   An electrophotographic apparatus comprising: the charging member according to claim 1; and a photosensitive member disposed in contact with the charging member.

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