WO2020230394A1 - Conductive endless belt - Google Patents

Conductive endless belt Download PDF

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Publication number
WO2020230394A1
WO2020230394A1 PCT/JP2020/006605 JP2020006605W WO2020230394A1 WO 2020230394 A1 WO2020230394 A1 WO 2020230394A1 JP 2020006605 W JP2020006605 W JP 2020006605W WO 2020230394 A1 WO2020230394 A1 WO 2020230394A1
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WO
WIPO (PCT)
Prior art keywords
belt
mass
resin
endless belt
carbon black
Prior art date
Application number
PCT/JP2020/006605
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French (fr)
Japanese (ja)
Inventor
佐伯　智
達也 裏川
Original Assignee
株式会社ブリヂストン
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Publication of WO2020230394A1 publication Critical patent/WO2020230394A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G15/00—Apparatus for electrographic processes using a charge pattern
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G15/00—Apparatus for electrographic processes using a charge pattern
    • G03G15/14—Apparatus for electrographic processes using a charge pattern for transferring a pattern to a second base
    • G03G15/16—Apparatus for electrographic processes using a charge pattern for transferring a pattern to a second base of a toner pattern, e.g. a powder pattern, e.g. magnetic transfer

Definitions

  • the present invention supplies a developer to the surface of an image forming body such as a latent image holder that holds an electrostatic latent image on the surface in an electrostatic recording process in an electrophotographic device such as a copier or a printer or an electrostatic recording device.
  • the present invention relates to a conductive endless belt (hereinafter, also simply referred to as “belt”) used when transferring the toner image formed in the above process to a recording medium such as paper.
  • the surface of a photoconductor (latent image holder) is first uniformly charged, and an image is projected onto the photoconductor from an optical system to expose it to light.
  • An electrostatic latent image is formed by erasing the charge on the portion, and then toner is supplied to the electrostatic latent image to form a toner image by electrostatic adhesion of the toner, which is used as paper, OHP, or printing paper.
  • a method of printing is adopted by transferring to a recording medium such as.
  • a printing method for forming a color image using an endless transfer belt as shown in FIG. 2 is known.
  • the first developing units 12a to the fourth developing units 12d which develop the electrostatic latent images on the photoconductor drums 11a to 11d with yellow, magenta, cyan, and black, respectively, are sequentially arranged along the transfer belt 10.
  • the transfer belt 10 is circulated and driven in the direction of the arrow in the drawing to sequentially transfer the four-color toner images formed on the photoconductor drums 11a to 11d of the developing units 12a to 12d, thereby sequentially transferring the toner images of four colors on the transfer belt 10.
  • a color toner image is formed on the surface, and the toner image is transferred onto a recording medium 13 such as paper to print out.
  • a recording medium 13 such as paper to print out.
  • the arrangement order of the toners used for development is not particularly limited and can be arbitrarily selected.
  • reference numeral 14 indicates a drive roller or tension roller for circulatingly driving the transfer belt 10
  • 15 is a secondary transfer roller
  • 16 is a recording medium feeder
  • 17 is a heating image on the recording medium, and the like.
  • the fixing device to be fixed by is shown.
  • Patent Document 1 describes an endless belt used in an image forming apparatus, in which 0.1 to 30 weights of a conductive substance is added to 100 parts by weight of a thermoplastic polymer component composed of a thermoplastic elastomer and a thermoplastic resin.
  • a polymer having a melt flow rate (MFR) value (190 ° C., 2.16 kgf load) according to JIS K7210 in the range of 0.01 to 10 g / 10 minutes was added to 100 parts by weight of the thermoplastic polymer component.
  • MFR melt flow rate
  • the four-color toner image in each developing unit is transferred onto the belt by the applied voltage at the time of transferring the toner image from the belt to the recording medium (secondary transfer) (secondary transfer).
  • a transfer mechanism that performs up to (primary transfer) may be adopted.
  • the belt applied to such an image forming apparatus is further required to have low electrical resistance in the belt circumferential direction, which is the driving direction of the belt.
  • an object of the present invention is to solve the above problems and provide a conductive endless belt having a predetermined volume resistivity and a surface resistivity in the belt circumferential direction.
  • the present invention relates to an endless belt-shaped conductive endless belt used in an image forming apparatus.
  • Contains base resin and carbon black The base resin is composed of a thermoplastic polybutylene terephthalate resin, a thermoplastic polybutylene naphthalate resin, and a thermoplastic polybutylene naphthalate elastomer.
  • the carbon black an average particle diameter was at 15nm or more 30nm or less, in which a DBP oil absorption amount is equal to or less than 150 cm 3/100 g or more 300 cm 3/100 g.
  • the belt of the present invention preferably contains the thermoplastic polybutylene terephthalate resin in an amount of 36% by mass or more based on the total amount of the base resin. Further, in the belt of the present invention, the mass ratio of the thermoplastic polybutylene naphthalate resin and the thermoplastic polybutylene terephthalate resin is preferably in the range of 0.64 to 1.5.
  • the carbon black is contained in an amount of 5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the base resin.
  • the belt of the present invention may further contain talc in an amount of 3 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the base resin.
  • the belt of the present invention is particularly useful as a transfer belt.
  • FIG. 1A and 1B are cross-sectional views in the width direction showing a configuration example of the conductive endless belt of the present invention.
  • the endless belt-shaped conductive endless belt generally has a joint and a non-joint (so-called seamless belt), but in the present invention, any of them may be used, and a seamless belt is preferable. is there.
  • the conductive endless belt of the present invention can be used as a transfer belt or the like in an image forming apparatus such as a copying machine or a printer.
  • the transfer belt 10 shown in FIG. 2 When the conductive endless belt of the present invention is, for example, the transfer belt 10 shown in FIG. 2, it is arranged between the developing units 12a to 12d provided with the photoconductor drums 11a to 11d and the recording medium 13 such as paper. , The four-color toner images formed on the surfaces of the photoconductor drums 11a to 11d, which are circulated and driven by a driving member such as a driving roller 14, are once transferred and held, and then transferred to the recording medium 13. Form a color image.
  • a driving member such as a driving roller 14
  • the belt of the present invention contains a base resin and carbon black
  • the base resin is a thermoplastic polybutylene terephthalate (PBT) resin, a thermoplastic polybutylene naphthalate (PBN) resin, and a thermoplastic polybutylene naphthalate (PBN).
  • PBT thermoplastic polybutylene terephthalate
  • PBN thermoplastic polybutylene naphthalate
  • PBN thermoplastic polybutylene naphthalate
  • PBN thermoplastic polybutylene naphthalate
  • the belt circumferential direction is satisfied while satisfying a predetermined volume resistivity. It has become possible to realize a belt in which the surface resistivity is low and electricity easily flows in the circumferential direction of the belt.
  • the carbon black is unevenly dispersed in the base resin, and the carbon black particles are connected and formed.
  • the structures (aggregates) to be formed are oriented along the surface of the belt.
  • the average particle size of carbon black is less than 15 nm, high conductivity is exhibited even with a very small amount of addition, so even a slight variation in the amount of addition causes a large variation in the resistance value, making it difficult to adjust to a predetermined resistance.
  • it exceeds 30 nm the surface resistivity in the circumferential direction of the belt cannot be sufficiently lowered, and in any case, the desired effect of the present invention cannot be obtained.
  • the average particle diameter is preferably is at 20nm or more 25nm or less, DBP oil absorption, suitably up to 155cm 3/100 g or more 200 cm 3/100 g.
  • the average particle size of carbon black is the arithmetic average particle size.
  • the amount of DBP oil absorbed is measured by the method described in JIS K 6217-4: 2008 and is indicated by the volume of dibutyl phthalate (DBP) absorbed per 100 g of carbon black.
  • the carbon black used in the present invention is not particularly limited in its production method and type as long as it satisfies the above average particle size and DBP oil absorption.
  • furnace black produced by the furnace method can be preferably used.
  • the blending amount of carbon black in the belt of the present invention is preferably 5 parts by mass or more and 20 parts by mass or less, and more preferably 7 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the base resin. Particularly preferably, it is 9 parts by mass or more and 13 parts by mass or less. According to the present invention, a desired volume resistivity and surface resistivity can be achieved at the same time with a relatively small amount of carbon black in the above range.
  • the base resin is made of a thermoplastic PBT resin, a thermoplastic PBN resin and a thermoplastic PBN elastomer.
  • the thermoplastic PBN elastomer in addition to the thermoplastic PBT resin and the thermoplastic PBN resin, the belt can be softened and the belt durability such as breakage resistance can be improved.
  • the blending amount of the thermoplastic PBN elastomer in the belt of the present invention is preferably 40% by mass or less, more preferably 5% by mass, based on the total amount of the base resin. It is 30% by mass or less.
  • the belt of the present invention preferably contains 36% by mass or more of the thermoplastic PBT resin with respect to the total amount of the base resin.
  • the electric resistance does not fluctuate due to a change in voltage in order to exhibit stable performance even if the usage environment changes.
  • a belt whose electrical resistance is voltage-dependent may be required.
  • thermoplastic PBT resin as 36% by mass or more with respect to the total amount of the base resin, carbon black is unevenly distributed in the base resin, and the electrical resistance becomes voltage-dependent. It can be a certain belt.
  • the content of the thermoplastic PBT resin is preferably 36% by mass or more, more preferably 36% by mass or more and 60% by mass or less, and 36% by mass or more and 44% by mass or less, based on the total amount of the base resin. Is particularly preferable.
  • the mass ratio of the thermoplastic PBN resin to the thermoplastic PBT resin is in the range of 0.64 to 1.5. Is preferable.
  • the mass ratio of the thermoplastic PBN resin and the thermoplastic PBT resin within the above range, in addition to the above effects, an effect of suppressing the occurrence of belt curl can be obtained.
  • the curl refers to a phenomenon in which a mark is left on the belt due to the shape in which the belt is fixed when the belt is fixed for a certain period of time.
  • the blending amount of the thermoplastic PBN resin may be, for example, 46% by mass or more and 54% by mass or less with respect to the total amount of the base resin. preferable.
  • the belt of the present invention can further contain talc in an amount of 3 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the base resin.
  • talc is insulating and has a scaly shape, so by blending talc, the insulating talc is stretched and oriented in the in-plane direction during molding, and a carbon black conductive path is formed in the plane direction. It is considered to be because it is limited.
  • the blending amount of talc is preferably 3 parts by mass or more and 20 parts by mass or less, and more preferably 5 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the base resin.
  • the average particle size of talc used in the present invention is preferably 1 ⁇ m or more and 20 ⁇ m or less, and more preferably 3 ⁇ m or more and 10 ⁇ m or less.
  • talc having an average particle size in the above range, the desired effect of the present invention can be satisfactorily obtained, which is preferable.
  • a median diameter D50 can be used, and for example, it can be measured by a laser light scattering method.
  • another conductive agent may be blended in order to adjust the conductivity.
  • the conductive agent is not particularly limited, and a known electronic conductive agent, ionic conductive agent, or the like can be appropriately used.
  • the electronic conductive agent specifically includes, for example, natural graphite, artificial graphite, antimony-doped tin oxide, titanium oxide, zinc oxide, nickel, copper, silver, germanium and other metals and metal oxides, polyaniline, polypyrrole. , Polyacetylene and other conductive polymers, carbon whiskers, graphite whiskers, titanium carbide whiskers, conductive potassium titanate whiskers, conductive barium titanate whiskers, conductive titanium oxide whiskers, conductive zinc oxide whiskers, etc. Can be mentioned.
  • ionic conductive agent examples include perchlorates such as tetraethylammonium, tetrabutylammonium, dodecyltrimethylammonium, hexadecyltrimethylammonium, benzyltrimethylammonium and modified fatty acid dimethylethylammonate, and chlorates.
  • Ammonites such as hydrochlorides, bromines, iodates, borohydrides, sulfates, ethyl sulfates, carboxylates, sulfonates, alkali metals such as lithium, sodium, potassium, calcium, magnesium , Alkaline earth metal perchlorate, chlorate, hydrochloride, bromine, iodiate, borohydrophosphite, sulfate, trifluoromethylsulfate, sulfonate and the like.
  • the other conductive agents may be used alone or in combination of two or more, and for example, an electronic conductive agent and an ionic conductive agent may be used in combination. In this case, it is possible to stably develop conductivity even with fluctuations in the applied voltage and changes in the environment.
  • the total amount of the electronic conductive agent including the carbon black is usually 100 parts by mass or less with respect to 100 parts by mass of the base resin, for example, 1 to 100 parts by mass. Of these, 1 to 80 parts by mass is preferable, and 5 to 50 parts by mass is particularly preferable.
  • the amount of the ionic conductive agent is usually 0.01 to 10 parts by mass, particularly preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the base resin.
  • polyester-based materials such as thermoplastic PBT resin, thermoplastic PBN resin, and thermoplastic PBN elastomer used as the base resin in the present invention have a drawback that they tend to cause a decrease in molecular weight due to hydrolysis during molding and heating. Therefore, it is preferable to add a compound having a carbodiimide group to the belt of the present invention and recrosslink the polyester-based material by the reaction between the carbodiimide group and the carboxylic acid to suppress the decrease in molecular weight. As a result, embrittlement of the belt can be prevented, and the crack resistance of the belt during durability can be improved.
  • Such a carbodiimide compound is easily available on the market, and examples thereof include the trade name carbodilite manufactured by Nisshinbo Chemical Co., Ltd.
  • the carbodiimide compound can also be used in the form of pellets or the like that have been master-batched in advance.
  • the trade names carbodilite E pellets and B pellets manufactured by Nisshinbo Chemical Co., Ltd. can be preferably used.
  • the amount of the carbodiimide compound added is not particularly limited, but is preferably 0.05 to 30 parts by mass, and more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the base resin. Is inside.
  • the belt of the present invention may appropriately contain other functional components in addition to the above-mentioned components as long as the effects of the present invention are not impaired.
  • Such other functional components include, for example, various fillers, reinforcing materials, flame retardants, antioxidants, compatibilizers, coupling agents, lubricants, surface treatment agents, pigments, ultraviolet absorbers, antistatic agents. , Dispersant, neutralizer, foaming agent, cross-linking agent and the like. Further, a colorant may be added for coloring.
  • the volume resistivity is in the range of 10 9 to 10 11 ⁇ ⁇ cm, and the surface resistivity is in the range of 10 6.5 to 10 8.5 ⁇ / ⁇ . Can be adjusted within.
  • the thickness of the belt of the present invention is appropriately selected according to the form of the applied member or the like, but is preferably in the range of 50 to 200 ⁇ m.
  • the surface roughness thereof is preferably 10 ⁇ m or less, particularly 6 ⁇ m or less, and further 3 ⁇ m or less in JIS 10-point average roughness Rz.
  • the tensile elastic modulus of the belt of the present invention is preferably 1000 MPa or more, particularly 1500 to 3000 MPa.
  • the belt of the present invention is formed on the drive member on the surface of the image forming apparatus of FIG. 2 on the side in contact with the drive member such as the drive roller 14.
  • a fitting portion that fits with the fitting portion (not shown) may be formed.
  • such a fitting portion is provided, and the fitting portion (not shown) provided on the drive member is fitted and run to run the conductive endless belt in the width direction of the conductive endless belt. It is possible to prevent the deviation of the belt.
  • the fitting portion is not particularly limited, but as shown in FIGS.
  • a continuous ridge is formed along the circumferential direction (rotational direction) of the belt, and this is a drive roller or the like. It is preferable that the drive member is fitted into a groove formed along the circumferential direction on the peripheral surface of the drive member.
  • FIG. 1A an example in which one continuous convex strip is provided as a fitting portion is shown, but in this fitting portion, a large number of convex portions are arranged in a row along the circumferential direction (rotation direction) of the belt. It may be provided so as to project, two or more fitting portions may be provided (FIG. 1B), or may be provided at the central portion in the width direction of the belt. Further, instead of the ridges shown in FIGS. 1A and 1B as the fitting portion, a groove is provided along the circumferential direction (rotational direction) of the belt, and this is provided in the circumferential direction on the peripheral surface of the drive member such as the drive roller. It may be fitted with the ridges formed along the line.
  • the belt of the present invention can be suitably produced by extrusion molding of a resin composition containing the above-mentioned base material resin and carbon black, and specifically, for example, the above-mentioned base material resin and carbon black by a twin-screw kneader. It can be produced by kneading a resin composition containing various compounding components of the above and extruding the obtained kneaded product using an annular die. Alternatively, a powder coating method such as electrostatic coating, a dip method or a centrifugal casting method can also be preferably adopted.
  • the belt of the present invention when the belt of the present invention is manufactured by extrusion molding, it is considered that carbon black and talc are likely to be oriented in the extrusion direction or the direction in which the inner diameter of the belt is expanded, that is, along the belt surface, which is preferable.
  • the resin composition containing the base resin and carbon black was mixed and dispersed with a twin-screw kneader to obtain pellets.
  • an endless shape transfer belt was formed with an inner diameter of 220 mm, a thickness of 100 ⁇ m, and a width of 250 mm by extrusion molding with a molding machine equipped with a cylindrical die at the tip of a single-screw extruder. ..
  • the blending amount in Table 1 indicates a part by mass.
  • volume resistivity ⁇ Measurement of volume resistivity>
  • a high-resta UP MCP-HT450 manufactured by Mitsubishi Chemical Analytech Co., Ltd.
  • a UR probe connected to it was used as a measuring device, and measurement was performed at a voltage of 250 V.
  • the volume resistivity was determined as the average value of the values measured at 20 points at a pitch of 30 mm. The results are shown in digits.
  • ⁇ Measurement of surface resistivity> A measurement was performed at a temperature of 23 ° C. and a relative humidity of 50% using a resistivity meter Hiresta (probe UR-100) manufactured by Mitsubishi Chemical Corporation at a voltage of 250 V, an application time of 10 seconds, and a pitch of 30 mm in the circumferential direction.
  • the surface resistivity in the circumferential direction of the belt was determined as the average value of the values measured at 20 points in. The results are shown in digits.
  • the base resin is made of a thermoplastic PBT resin, a thermoplastic PBN resin, and a thermoplastic PBN elastomer, and the average particle size of carbon black and the DBP oil absorption amount are within a predetermined range. It was confirmed that the surface resistivity in the circumferential direction of the belt can be lowered when the volume resistivity is kept constant. It was also confirmed that the above effect can be obtained while suppressing the amount of carbon black blended by further blending talc.

Abstract

The present invention provides a conductive endless belt which has a specific volume resistivity and a specific surface resistivity in the belt circumferential direction at the same time.　The present invention is a conductive endless belt having an endless belt shape, which is used in an image forming apparatus. This conductive endless belt contains a base material resin and carbon black; the base material resin is composed of a thermoplastic polybutylene terephthalate resin, a thermoplastic polybutylene naphthalate resin and a thermoplastic polybutylene naphthalate elastomer; and the carbon black has an average particle diameter of from 15 nm to 30 nm (inclusive) and a DBP oil absorption of from 150 cm3/100 g to 300 cm3/100 g (inclusive).

Description

導電性エンドレスベルトConductive endless belt
　本発明は、複写機、プリンタ等の電子写真装置や静電記録装置等における静電記録プロセスにおいて、表面に静電潜像を保持した潜像保持体等の画像形成体表面に現像剤を供給して形成されたトナー像を、紙等の記録媒体へと転写する際に用いられる導電性エンドレスベルト（以下、単に「ベルト」とも称する）に関する。 The present invention supplies a developer to the surface of an image forming body such as a latent image holder that holds an electrostatic latent image on the surface in an electrostatic recording process in an electrophotographic device such as a copier or a printer or an electrostatic recording device. The present invention relates to a conductive endless belt (hereinafter, also simply referred to as “belt”) used when transferring the toner image formed in the above process to a recording medium such as paper.
　従来から、複写機やプリンタ等における静電記録プロセスでは、まず、感光体（潜像保持体）の表面を一様に帯電させ、この感光体に光学系から映像を投射して光の当たった部分の帯電を消去することによって静電潜像を形成し、次いで、この静電潜像にトナーを供給してトナーの静電的付着によりトナー像を形成し、これを紙、ＯＨＰ、印画紙等の記録媒体へと転写することにより、プリントする方法が採られている。 Conventionally, in the electrostatic recording process in copiers, printers, etc., the surface of a photoconductor (latent image holder) is first uniformly charged, and an image is projected onto the photoconductor from an optical system to expose it to light. An electrostatic latent image is formed by erasing the charge on the portion, and then toner is supplied to the electrostatic latent image to form a toner image by electrostatic adhesion of the toner, which is used as paper, OHP, or printing paper. A method of printing is adopted by transferring to a recording medium such as.
　この場合、カラーレーザープリンタやカラー複写機においても、基本的には前記プロセスに従ってプリントが行われるが、カラー印刷の場合には、例えば、マゼンタ、イエロー、シアン、ブラックの４色のトナーを用いて色調を再現する。そのため、これらのトナーを所定割合で重ね合わせて必要な色調を得るための工程が必要であり、この工程を行うためにいくつかの方式が提案されている。 In this case, even in a color laser printer or a color copier, printing is basically performed according to the above process, but in the case of color printing, for example, four color toners of magenta, yellow, cyan, and black are used. Reproduce the color tone. Therefore, a step of superimposing these toners at a predetermined ratio to obtain a required color tone is required, and several methods have been proposed for performing this step.
　中でも、汎用の方式として、図２に示すような無端状の転写ベルトを用いてカラー画像の形成を行うプリント方式が知られている。図示する装置においては、感光体ドラム１１ａ～１１ｄ上の静電潜像を夫々イエロー、マゼンタ、シアン、ブラックにより現像する第１現像部１２ａ～第４現像部１２ｄが転写ベルト１０に沿って順次配置されている。この転写ベルト１０を図中の矢印方向に循環駆動させて、各現像部１２ａ～１２ｄの感光体ドラム１１ａ～１１ｄ上に形成された４色のトナー像を順次転写することにより、転写ベルト１０上にカラーのトナー像を形成し、このトナー像を紙等の記録媒体１３上に転写することにより、プリントアウトを行う。ここで、図示する装置において、現像に用いるトナーの配列順は特に制限されるものではなく、任意に選択可能である。また、図中、符号１４は、転写ベルト１０を循環駆動するための駆動ローラまたはテンションローラを示し、１５は２次転写ローラ、１６は記録媒体送り装置、１７は記録媒体上の画像を加熱等により定着させる定着装置を示す。 Among them, as a general-purpose method, a printing method for forming a color image using an endless transfer belt as shown in FIG. 2 is known. In the illustrated device, the first developing units 12a to the fourth developing units 12d, which develop the electrostatic latent images on the photoconductor drums 11a to 11d with yellow, magenta, cyan, and black, respectively, are sequentially arranged along the transfer belt 10. Has been done. The transfer belt 10 is circulated and driven in the direction of the arrow in the drawing to sequentially transfer the four-color toner images formed on the photoconductor drums 11a to 11d of the developing units 12a to 12d, thereby sequentially transferring the toner images of four colors on the transfer belt 10. A color toner image is formed on the surface, and the toner image is transferred onto a recording medium 13 such as paper to print out. Here, in the apparatus shown in the figure, the arrangement order of the toners used for development is not particularly limited and can be arbitrarily selected. Further, in the figure, reference numeral 14 indicates a drive roller or tension roller for circulatingly driving the transfer belt 10, 15 is a secondary transfer roller, 16 is a recording medium feeder, 17 is a heating image on the recording medium, and the like. The fixing device to be fixed by is shown.
　このような電子写真方式の画像形成プロセスにおいて使用可能なベルトの基材樹脂としては、従来、熱可塑性樹脂が汎用されている。例えば、特許文献１には、画像形成装置に用いられるエンドレスベルトであって、熱可塑性エラストマーと熱可塑性樹脂とからなる熱可塑性ポリマー成分１００重量部に対して導電性物質を０．１～３０重量部含み、更に、ＪＩＳ　Ｋ７２１０によるメルトフローレート（ＭＦＲ）値（１９０℃、２．１６ｋｇｆ荷重）が０．０１～１０ｇ／１０分の範囲の値を示すポリマーを、熱可塑性ポリマー成分１００重量部に対して０．０１～２０重量部含む画像形成装置用ベルトが開示されている。 Conventionally, a thermoplastic resin has been widely used as a base resin for a belt that can be used in such an electrophotographic image forming process. For example, Patent Document 1 describes an endless belt used in an image forming apparatus, in which 0.1 to 30 weights of a conductive substance is added to 100 parts by weight of a thermoplastic polymer component composed of a thermoplastic elastomer and a thermoplastic resin. A polymer having a melt flow rate (MFR) value (190 ° C., 2.16 kgf load) according to JIS K7210 in the range of 0.01 to 10 g / 10 minutes was added to 100 parts by weight of the thermoplastic polymer component. On the other hand, a belt for an image forming apparatus containing 0.01 to 20 parts by weight is disclosed.
特開２００５－８４２４７号公報Japanese Unexamined Patent Publication No. 2005-84247
　一般に、このようなベルトにおいては、トナー像を記録媒体上に確実に転写するために、所定の体積抵抗率を満足することが要求される。その一方、画像形成装置の構成によっては、ベルトから記録媒体上へのトナー像の転写（２次転写）の際の印加電圧によって、各現像部における４色のトナー像のベルト上への転写（１次転写）までを行う転写機構を採用する場合がある。このような画像形成装置に適用するベルトには、さらに、ベルトの駆動方向であるベルト周方向における電気抵抗が低いことが求められる。 Generally, in such a belt, it is required to satisfy a predetermined volume resistivity in order to reliably transfer the toner image onto the recording medium. On the other hand, depending on the configuration of the image forming apparatus, the four-color toner image in each developing unit is transferred onto the belt by the applied voltage at the time of transferring the toner image from the belt to the recording medium (secondary transfer) (secondary transfer). A transfer mechanism that performs up to (primary transfer) may be adopted. The belt applied to such an image forming apparatus is further required to have low electrical resistance in the belt circumferential direction, which is the driving direction of the belt.
　しかしながら、特許文献１に開示されたベルトにおいては、ベルト周方向における電気抵抗については考慮されておらず、上記要求性能を満足できるものではなかった。 However, in the belt disclosed in Patent Document 1, the electrical resistance in the belt circumferential direction is not taken into consideration, and the above required performance cannot be satisfied.
　そこで本発明の目的は、上記問題を解消して、所定の体積抵抗率およびベルト周方向における表面抵抗率を兼ね備えた導電性エンドレスベルトを提供することにある。 Therefore, an object of the present invention is to solve the above problems and provide a conductive endless belt having a predetermined volume resistivity and a surface resistivity in the belt circumferential direction.
　本発明者らは、鋭意検討した結果、特定の熱可塑性樹脂の組合せを含む基材樹脂に対し、ストラクチャの発達したカーボンブラックを配合することにより、上記課題を解決できることを見出して、本発明を完成するに至った。 As a result of diligent studies, the present inventors have found that the above problems can be solved by blending carbon black with a developed structure with a base resin containing a specific combination of thermoplastic resins, and have found that the present invention can be solved. It came to be completed.
　すなわち、本発明は、画像形成装置に用いられる無端ベルト状の導電性エンドレスベルトにおいて、
　基材樹脂とカーボンブラックとを含有し、
　前記基材樹脂が、熱可塑性ポリブチレンテレフタレート樹脂、熱可塑性ポリブチレンナフタレート樹脂および熱可塑性ポリブチレンナフタレートエラストマーからなるとともに、
　前記カーボンブラックの、平均粒子径が１５ｎｍ以上３０ｎｍ以下であって、ＤＢＰ吸油量が１５０ｃｍ３／１００ｇ以上３００ｃｍ３／１００ｇ以下であることを特徴とするものである。 That is, the present invention relates to an endless belt-shaped conductive endless belt used in an image forming apparatus.
Contains base resin and carbon black,
The base resin is composed of a thermoplastic polybutylene terephthalate resin, a thermoplastic polybutylene naphthalate resin, and a thermoplastic polybutylene naphthalate elastomer.
Wherein the carbon black, an average particle diameter was at 15nm or more 30nm or less, in which a DBP oil absorption amount is equal to or less than 150 cm 3/100 g or more 300 cm 3/100 g.
　本発明のベルトにおいては、前記基材樹脂の全量に対し、前記熱可塑性ポリブチレンテレフタレート樹脂を３６質量％以上含有することが好ましい。また、本発明のベルトにおいては、前記熱可塑性ポリブチレンナフタレート樹脂と前記熱可塑性ポリブチレンテレフタレート樹脂との質量比率が、０．６４～１．５の範囲内であることが好ましい。 The belt of the present invention preferably contains the thermoplastic polybutylene terephthalate resin in an amount of 36% by mass or more based on the total amount of the base resin. Further, in the belt of the present invention, the mass ratio of the thermoplastic polybutylene naphthalate resin and the thermoplastic polybutylene terephthalate resin is preferably in the range of 0.64 to 1.5.
　さらに、本発明のベルトにおいては、前記基材樹脂１００質量部に対し、前記カーボンブラックを５質量部以上２０質量部以下で含有することが好ましい。さらにまた、本発明のベルトにおいては、前記基材樹脂１００質量部に対し、さらに、タルクを３質量部以上２０質量部以下で含有するものとすることもできる。 Further, in the belt of the present invention, it is preferable that the carbon black is contained in an amount of 5 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the base resin. Furthermore, the belt of the present invention may further contain talc in an amount of 3 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the base resin.
　本発明のベルトは、特に、転写ベルトとして有用である。 The belt of the present invention is particularly useful as a transfer belt.
　本発明によれば、上記構成としたことで、所定の体積抵抗率およびベルト周方向における表面抵抗率を兼ね備えた導電性エンドレスベルトを実現することができた。 According to the present invention, with the above configuration, it is possible to realize a conductive endless belt having a predetermined volume resistivity and a surface resistivity in the belt circumferential direction.
本発明の導電性エンドレスベルトの一構成例を示す幅方向断面図である。It is a cross-sectional view in the width direction which shows one structural example of the conductive endless belt of this invention. 本発明の導電性エンドレスベルトの他の構成例を示す幅方向断面図である。It is sectional drawing in the width direction which shows the other structural example of the conductive endless belt of this invention. 本発明に係る画像形成装置の一例を示す概略図である。It is the schematic which shows an example of the image forming apparatus which concerns on this invention.
　以下、本発明の実施の形態について、図面を参照しつつ詳細に説明する。
　図１Ａ，１Ｂは、本発明の導電性エンドレスベルトの一構成例を示す幅方向断面図である。無端ベルト状の導電性エンドレスベルトには、一般に、ジョイントありのものとジョイントなしのもの（いわゆるシームレスベルト）とがあるが、本発明においてはいずれのものであってもよく、好ましくはシームレスベルトである。本発明の導電性エンドレスベルトは、複写機やプリンタ等の画像形成装置において、転写ベルト等として用いることができるものである。 Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
1A and 1B are cross-sectional views in the width direction showing a configuration example of the conductive endless belt of the present invention. The endless belt-shaped conductive endless belt generally has a joint and a non-joint (so-called seamless belt), but in the present invention, any of them may be used, and a seamless belt is preferable. is there. The conductive endless belt of the present invention can be used as a transfer belt or the like in an image forming apparatus such as a copying machine or a printer.
　本発明の導電性エンドレスベルトが、例えば、図２に示す転写ベルト１０である場合、感光体ドラム１１ａ～１１ｄを備える現像部１２ａ～１２ｄと紙等の記録媒体１３との間に配設されて、駆動ローラ１４等の駆動部材により循環駆動され、各感光体ドラム１１ａ～１１ｄの表面に形成された４色のトナー像を一旦転写保持し、次いでこれを記録媒体１３へと転写することで、カラー画像を形成する。なお、ここではトナーが４色の場合について説明しているが、トナーの色数が４色に限られないことは言うまでもない。 When the conductive endless belt of the present invention is, for example, the transfer belt 10 shown in FIG. 2, it is arranged between the developing units 12a to 12d provided with the photoconductor drums 11a to 11d and the recording medium 13 such as paper. , The four-color toner images formed on the surfaces of the photoconductor drums 11a to 11d, which are circulated and driven by a driving member such as a driving roller 14, are once transferred and held, and then transferred to the recording medium 13. Form a color image. Although the case where the toner has four colors is described here, it goes without saying that the number of toner colors is not limited to four.
　本発明のベルトは、基材樹脂とカーボンブラックとを含有し、基材樹脂が、熱可塑性ポリブチレンテレフタレート（ＰＢＴ）樹脂、熱可塑性ポリブチレンナフタレート（ＰＢＮ）樹脂および熱可塑性ポリブチレンナフタレート（ＰＢＮ）エラストマーからなるとともに、カーボンブラックの、平均粒子径が１５ｎｍ以上３０ｎｍ以下であって、ＤＢＰ吸油量（吸収量）が１５０ｃｍ３／１００ｇ以上３００ｃｍ３／１００ｇ以下である点に特徴を有する。本発明によれば、特定の組合せからなる基材樹脂とともに、特定の平均粒子径およびＤＢＰ吸油量を有するカーボンブラックを用いるものとしたことで、所定の体積抵抗率を満足しつつ、ベルト周方向における表面抵抗率が低く、ベルト周方向に電気の流れやすいベルトを実現することが可能となった。 The belt of the present invention contains a base resin and carbon black, and the base resin is a thermoplastic polybutylene terephthalate (PBT) resin, a thermoplastic polybutylene naphthalate (PBN) resin, and a thermoplastic polybutylene naphthalate (PBN). together consisting PBN) elastomers, carbon black, an average particle diameter was at 15nm or more 30nm or less, DBP oil absorption (absorption amount) having a feature that is not more than 150 cm 3/100 g or more 300 cm 3/100 g. According to the present invention, by using carbon black having a specific average particle size and DBP oil absorption amount together with a base resin composed of a specific combination, the belt circumferential direction is satisfied while satisfying a predetermined volume resistivity. It has become possible to realize a belt in which the surface resistivity is low and electricity easily flows in the circumferential direction of the belt.
　本発明においては、上記平均粒子径およびＤＢＰ吸油量を満足するストラクチャの発達したカーボンブラックを用いることで、基材樹脂中でカーボンブラックが不均一に分散して、カーボンブラックの粒子がつながって形成されるストラクチャ（凝集体）がベルトの面に沿って配向する。これにより、ベルト厚み方向の電気抵抗を示すベルトの体積抵抗率を一定にした場合に、ベルトの面内方向の抵抗に係る表面抵抗率を、より低くすることができ、面内方向、特にはベルト周方向において、電気を流れやすくすることができるものと考えられる。 In the present invention, by using carbon black having a developed structure that satisfies the above average particle size and DBP oil absorption amount, the carbon black is unevenly dispersed in the base resin, and the carbon black particles are connected and formed. The structures (aggregates) to be formed are oriented along the surface of the belt. As a result, when the volume resistivity of the belt, which indicates the electrical resistance in the belt thickness direction, is made constant, the surface resistivity related to the in-plane resistance of the belt can be made lower, and the in-plane direction, particularly It is considered that electricity can easily flow in the circumferential direction of the belt.
　カーボンブラックの平均粒子径が、１５ｎｍ未満であると、ごく少量の添加でも高導電性を発現するため、添加量のわずかなばらつきでも抵抗値が大きく変動し、所定の抵抗に調節するのが困難となり、一方、３０ｎｍを超えるとベルト周方向における表面抵抗率を十分低くできず、いずれにしても本発明の所期の効果が得られない。また、カーボンブラックのＤＢＰ吸油量が、１５０ｃｍ３／１００ｇ未満であるとベルト周方向における表面抵抗率を十分低くできず、一方、３００ｃｍ３／１００ｇを超えるとごく少量の添加でも高導電性を発現するため、添加量のわずかなばらつきでも抵抗値が大きく変動し、所定の抵抗に調節するのが困難となり、いずれにしても本発明の所期の効果が得られない。カーボンブラックの、平均粒子径は、好適には２０ｎｍ以上２５ｎｍ以下であり、ＤＢＰ吸油量は、好適には１５５ｃｍ３／１００ｇ以上２００ｃｍ３／１００ｇ以下である。なお、カーボンブラックの平均粒子径は算術平均粒子径である。また、ＤＢＰ吸油量は、ＪＩＳ　Ｋ　６２１７－４：２００８に記載の方法により測定され、カーボンブラック１００ｇ当たりに吸収されるジブチルフタレート（ＤＢＰ）の体積で表示される。 If the average particle size of carbon black is less than 15 nm, high conductivity is exhibited even with a very small amount of addition, so even a slight variation in the amount of addition causes a large variation in the resistance value, making it difficult to adjust to a predetermined resistance. On the other hand, if it exceeds 30 nm, the surface resistivity in the circumferential direction of the belt cannot be sufficiently lowered, and in any case, the desired effect of the present invention cannot be obtained. Further, DBP oil absorption of the carbon black can not be sufficiently low surface resistivity is less than 150 cm 3/100 g in the belt circumferential direction, whereas, express high conductivity even in a very small amount of addition exceeds 300 cm 3/100 g Therefore, even a slight variation in the amount of addition causes the resistance value to fluctuate greatly, making it difficult to adjust the resistance to a predetermined value, and in any case, the desired effect of the present invention cannot be obtained. Of carbon black, the average particle diameter is preferably is at 20nm or more 25nm or less, DBP oil absorption, suitably up to 155cm 3/100 g or more 200 cm 3/100 g. The average particle size of carbon black is the arithmetic average particle size. The amount of DBP oil absorbed is measured by the method described in JIS K 6217-4: 2008 and is indicated by the volume of dibutyl phthalate (DBP) absorbed per 100 g of carbon black.
　本発明において使用するカーボンブラックは、上記平均粒子径およびＤＢＰ吸油量を満足するものであれば、その製造方法や種類については、特に制限はない。例えば、ファーネス法で製造されたファーネスブラックを好適に用いることができる。 The carbon black used in the present invention is not particularly limited in its production method and type as long as it satisfies the above average particle size and DBP oil absorption. For example, furnace black produced by the furnace method can be preferably used.
　本発明のベルトにおけるカーボンブラックの配合量は、基材樹脂１００質量部に対し、好適には５質量部以上２０質量部以下であり、より好適には７質量部以上１５質量部以下であり、特に好適には９質量部以上１３質量部以下である。本発明によれば、上記範囲の比較的少ないカーボンブラックの配合量で、所望の体積抵抗率および表面抵抗率を両立させることができる。 The blending amount of carbon black in the belt of the present invention is preferably 5 parts by mass or more and 20 parts by mass or less, and more preferably 7 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the base resin. Particularly preferably, it is 9 parts by mass or more and 13 parts by mass or less. According to the present invention, a desired volume resistivity and surface resistivity can be achieved at the same time with a relatively small amount of carbon black in the above range.
　また、本発明のベルトは、基材樹脂が、熱可塑性ＰＢＴ樹脂、熱可塑性ＰＢＮ樹脂および熱可塑性ＰＢＮエラストマーからなる。熱可塑性ＰＢＴ樹脂および熱可塑性ＰＢＮ樹脂に加えて、熱可塑性ＰＢＮエラストマーを含有させることで、ベルトを柔らかくして、耐折れ性等のベルト耐久性を向上することができる。このような効果を良好に得るために、本発明のベルトにおける熱可塑性ＰＢＮエラストマーの配合量は、基材樹脂の全量に対し、好適には４０質量％以下であり、より好適には５質量％以上３０質量％以下である。 Further, in the belt of the present invention, the base resin is made of a thermoplastic PBT resin, a thermoplastic PBN resin and a thermoplastic PBN elastomer. By containing the thermoplastic PBN elastomer in addition to the thermoplastic PBT resin and the thermoplastic PBN resin, the belt can be softened and the belt durability such as breakage resistance can be improved. In order to obtain such an effect satisfactorily, the blending amount of the thermoplastic PBN elastomer in the belt of the present invention is preferably 40% by mass or less, more preferably 5% by mass, based on the total amount of the base resin. It is 30% by mass or less.
　また、本発明のベルトにおいては、基材樹脂の全量に対し、熱可塑性ＰＢＴ樹脂を３６質量％以上含有することが好ましい。通常、複写機やプリンタ等に搭載して使用されるベルトにおいては、使用環境が変化しても安定した性能を発揮させるために、電圧の変化によって電気抵抗が変動しないことが求められるが、装置側の仕様によっては、電気抵抗に電圧依存性があるベルトが求められる場合もある。本発明においては、基材樹脂の全量に対し、熱可塑性ＰＢＴ樹脂を３６質量％以上と多量で含有させることで、基材樹脂中においてカーボンブラックの偏在が生じて、電気抵抗に電圧依存性があるベルトとすることができる。熱可塑性ＰＢＴ樹脂の含有量は、基材樹脂の全量に対し、３６質量％以上とすることが好ましく、３６質量％以上６０質量％以下とすることがより好ましく、３６質量％以上４４質量％以下とすることが特に好ましい。 Further, the belt of the present invention preferably contains 36% by mass or more of the thermoplastic PBT resin with respect to the total amount of the base resin. Normally, in a belt mounted on a copier or a printer, it is required that the electric resistance does not fluctuate due to a change in voltage in order to exhibit stable performance even if the usage environment changes. Depending on the specifications on the side, a belt whose electrical resistance is voltage-dependent may be required. In the present invention, by containing a large amount of thermoplastic PBT resin as 36% by mass or more with respect to the total amount of the base resin, carbon black is unevenly distributed in the base resin, and the electrical resistance becomes voltage-dependent. It can be a certain belt. The content of the thermoplastic PBT resin is preferably 36% by mass or more, more preferably 36% by mass or more and 60% by mass or less, and 36% by mass or more and 44% by mass or less, based on the total amount of the base resin. Is particularly preferable.
　さらに、本発明においては、熱可塑性ＰＢＮ樹脂と熱可塑性ＰＢＴ樹脂との質量比率（熱可塑性ＰＢＮ樹脂の質量／熱可塑性ＰＢＴ樹脂の質量）が、０．６４～１．５の範囲内であることが好ましい。熱可塑性ＰＢＮ樹脂と熱可塑性ＰＢＴ樹脂との質量比率を上記範囲とすることにより、上記効果に加えてさらに、ベルトの巻癖の発生を抑制する効果を得ることができる。ここで、巻癖とは、ベルトを一定時間固定していた際に、ベルトを固定していた形状によって、ベルトに痕が残ってしまう現象をいう。熱可塑性ＰＢＮ樹脂と熱可塑性ＰＢＴ樹脂との上記質量比率を得るために、熱可塑性ＰＢＮ樹脂の配合量は、基材樹脂の全量に対し、例えば、４６質量％以上５４質量％以下とすることが好ましい。 Further, in the present invention, the mass ratio of the thermoplastic PBN resin to the thermoplastic PBT resin (mass of the thermoplastic PBN resin / mass of the thermoplastic PBT resin) is in the range of 0.64 to 1.5. Is preferable. By setting the mass ratio of the thermoplastic PBN resin and the thermoplastic PBT resin within the above range, in addition to the above effects, an effect of suppressing the occurrence of belt curl can be obtained. Here, the curl refers to a phenomenon in which a mark is left on the belt due to the shape in which the belt is fixed when the belt is fixed for a certain period of time. In order to obtain the above mass ratio of the thermoplastic PBN resin and the thermoplastic PBT resin, the blending amount of the thermoplastic PBN resin may be, for example, 46% by mass or more and 54% by mass or less with respect to the total amount of the base resin. preferable.
　本発明のベルトには、さらに、基材樹脂１００質量部に対し、タルクを３質量部以上２０質量部以下で含有させることができる。タルクを所定量で配合することで、カーボンブラックの配合量をさらに抑制しつつ、ベルト周方向における電気抵抗を低下させて、所望の体積抵抗率および表面抵抗率を有するベルトを得ることができる。これは、タルクは絶縁性であって鱗片状の形状を有するため、タルクを配合することで、成形時に絶縁性のあるタルクが面内方向に延伸配向し、面方向にカーボンブラックの導電パスが限定されるため、であると考えられる。 The belt of the present invention can further contain talc in an amount of 3 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the base resin. By blending talc in a predetermined amount, it is possible to obtain a belt having a desired volume resistivity and surface resistivity by further suppressing the blending amount of carbon black and reducing the electrical resistance in the belt circumferential direction. This is because talc is insulating and has a scaly shape, so by blending talc, the insulating talc is stretched and oriented in the in-plane direction during molding, and a carbon black conductive path is formed in the plane direction. It is considered to be because it is limited.
　タルクの配合量は、基材樹脂１００質量部に対し、好適には３質量部以上２０質量部以下、より好適には５質量部以上１５質量部以下である。タルクの配合量を上記範囲とすることで、ベルトの機械的強度の低下による耐久性能の低下を抑制しつつ、タルクを配合することによる効果を十分に得ることができる。 The blending amount of talc is preferably 3 parts by mass or more and 20 parts by mass or less, and more preferably 5 parts by mass or more and 15 parts by mass or less with respect to 100 parts by mass of the base resin. By setting the blending amount of talc within the above range, it is possible to sufficiently obtain the effect of blending talc while suppressing the deterioration of durability performance due to the decrease in mechanical strength of the belt.
　本発明に用いるタルクの平均粒子径は、好適には１μｍ以上２０μｍ以下であり、より好適には３μｍ以上１０μｍ以下である。上記範囲の平均粒子径を有するタルクを用いることで、本発明の所期の効果を良好に得ることができ、好ましい。ここで、タルクの平均粒子径としては、メディアン径Ｄ５０を用いることができ、例えば、レーザー光散乱法により測定することができる。 The average particle size of talc used in the present invention is preferably 1 μm or more and 20 μm or less, and more preferably 3 μm or more and 10 μm or less. By using talc having an average particle size in the above range, the desired effect of the present invention can be satisfactorily obtained, which is preferable. Here, as the average particle diameter of talc, a median diameter D50 can be used, and for example, it can be measured by a laser light scattering method.
　本発明のベルトにおいては、導電性を調整するために、カーボンブラックに加えて、他の導電剤を配合してもよい。このような導電剤としては、特に制限されるものではなく、公知の電子導電剤やイオン導電剤等を適宜用いることができる。 In the belt of the present invention, in addition to carbon black, another conductive agent may be blended in order to adjust the conductivity. The conductive agent is not particularly limited, and a known electronic conductive agent, ionic conductive agent, or the like can be appropriately used.
　このうち電子導電剤としては、具体的には例えば、天然グラファイト、人造グラファイト、アンチモンドープの酸化錫、酸化チタン、酸化亜鉛、ニッケル、銅、銀、ゲルマニウム等の金属および金属酸化物、ポリアニリン、ポリピロール、ポリアセチレン等の導電性ポリマー、カーボンウイスカー、黒鉛ウイスカー、炭化チタンウイスカー、導電性チタン酸カリウムウイスカー、導電性チタン酸バリウムウイスカー、導電性酸化チタンウイスカー、導電性酸化亜鉛ウイスカー等の導電性ウイスカー等が挙げられる。また、イオン導電剤としては、具体的には例えば、テトラエチルアンモニウム、テトラブチルアンモニウム、ドデシルトリメチルアンモニウム、ヘキサデシルトリメチルアンモニウム、ベンジルトリメチルアンモニウム、変性脂肪酸ジメチルエチルアンモニウム等の過塩素酸塩、塩素酸塩、塩酸塩、臭素酸塩、ヨウ素酸塩、ホウ弗化水素酸塩、硫酸塩、エチル硫酸塩、カルボン酸塩、スルホン酸塩などのアンモニウム塩、リチウム、ナトリウム、カリウム、カルシウム、マグネシウムなどのアルカリ金属、アルカリ土類金属の過塩素酸塩、塩素酸塩、塩酸塩、臭素酸塩、ヨウ素酸塩、ホウ弗化水素酸塩、硫酸塩、トリフルオロメチル硫酸塩、スルホン酸塩等が挙げられる。 Among these, the electronic conductive agent specifically includes, for example, natural graphite, artificial graphite, antimony-doped tin oxide, titanium oxide, zinc oxide, nickel, copper, silver, germanium and other metals and metal oxides, polyaniline, polypyrrole. , Polyacetylene and other conductive polymers, carbon whiskers, graphite whiskers, titanium carbide whiskers, conductive potassium titanate whiskers, conductive barium titanate whiskers, conductive titanium oxide whiskers, conductive zinc oxide whiskers, etc. Can be mentioned. Specific examples of the ionic conductive agent include perchlorates such as tetraethylammonium, tetrabutylammonium, dodecyltrimethylammonium, hexadecyltrimethylammonium, benzyltrimethylammonium and modified fatty acid dimethylethylammonate, and chlorates. Ammonites such as hydrochlorides, bromines, iodates, borohydrides, sulfates, ethyl sulfates, carboxylates, sulfonates, alkali metals such as lithium, sodium, potassium, calcium, magnesium , Alkaline earth metal perchlorate, chlorate, hydrochloride, bromine, iodiate, borohydrophosphite, sulfate, trifluoromethylsulfate, sulfonate and the like.
　本発明において、上記他の導電剤は、１種を単独で用いても、２種以上を適宜組み合わせて用いてもよく、例えば、電子導電剤とイオン導電剤とを組み合わせて用いることもでき、この場合、印加される電圧の変動や環境の変化に対しても安定して導電性を発現させることができる。 In the present invention, the other conductive agents may be used alone or in combination of two or more, and for example, an electronic conductive agent and an ionic conductive agent may be used in combination. In this case, it is possible to stably develop conductivity even with fluctuations in the applied voltage and changes in the environment.
　上記他の導電剤の配合量としては、電子導電剤については、上記カーボンブラックを含めた総量で、基材樹脂１００質量部に対し、通常１００質量部以下であり、例えば１～１００質量部とすることができ、中でも１～８０質量部が好ましく、特には５～５０質量部が好ましい。また、イオン導電剤については、基材樹脂１００質量部に対し、通常０．０１～１０質量部であり、特には０．０５～５質量部とすることが好ましい。 As for the blending amount of the other conductive agent, the total amount of the electronic conductive agent including the carbon black is usually 100 parts by mass or less with respect to 100 parts by mass of the base resin, for example, 1 to 100 parts by mass. Of these, 1 to 80 parts by mass is preferable, and 5 to 50 parts by mass is particularly preferable. The amount of the ionic conductive agent is usually 0.01 to 10 parts by mass, particularly preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the base resin.
　また、本発明において基材樹脂として用いる熱可塑性ＰＢＴ樹脂や熱可塑性ＰＢＮ樹脂、熱可塑性ＰＢＮエラストマー等のポリエステル系材料は、成形加熱時において加水分解による分子量低下を引き起こしやすいという難点がある。そのため、本発明のベルトには、カルボジイミド基を有する化合物を添加して、カルボジイミド基とカルボン酸との反応によりポリエステル系材料を再架橋させることで、分子量の低下を抑制することが好ましい。これにより、ベルトの脆化を防止することができ、耐久時におけるベルトの耐割れ性を向上することが可能となる。このようなカルボジイミド化合物は市場で容易に入手可能であり、例えば、日清紡ケミカル（株）製の商品名カルボジライト等を挙げることができる。また、カルボジイミド化合物は、あらかじめマスターバッチ化されたペレット等の形態でも用いることができ、例えば、日清紡ケミカル（株）製の商品名カルボジライトＥペレット、Ｂペレット等を好適に用いることができる。 Further, polyester-based materials such as thermoplastic PBT resin, thermoplastic PBN resin, and thermoplastic PBN elastomer used as the base resin in the present invention have a drawback that they tend to cause a decrease in molecular weight due to hydrolysis during molding and heating. Therefore, it is preferable to add a compound having a carbodiimide group to the belt of the present invention and recrosslink the polyester-based material by the reaction between the carbodiimide group and the carboxylic acid to suppress the decrease in molecular weight. As a result, embrittlement of the belt can be prevented, and the crack resistance of the belt during durability can be improved. Such a carbodiimide compound is easily available on the market, and examples thereof include the trade name carbodilite manufactured by Nisshinbo Chemical Co., Ltd. The carbodiimide compound can also be used in the form of pellets or the like that have been master-batched in advance. For example, the trade names carbodilite E pellets and B pellets manufactured by Nisshinbo Chemical Co., Ltd. can be preferably used.
　カルボジイミド化合物の添加量としては、特に制限されるものではないが、基材樹脂１００質量部に対し、好ましくは０．０５～３０質量部であり、より好ましくは０．１～５質量部の範囲内である。 The amount of the carbodiimide compound added is not particularly limited, but is preferably 0.05 to 30 parts by mass, and more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the base resin. Is inside.
　本発明のベルトには、本発明の効果を損なわない範囲で、上述の成分に加えて他の機能性成分を適宜配合することも可能である。このような他の機能性成分としては、例えば、各種充填材、補強材、難燃剤、酸化防止剤、相溶化剤、カップリング剤、滑剤、表面処理剤、顔料、紫外線吸収剤、帯電防止剤、分散剤、中和剤、発泡剤、架橋剤等を挙げることができる。さらに、着色剤を添加して着色を施してもよい。 The belt of the present invention may appropriately contain other functional components in addition to the above-mentioned components as long as the effects of the present invention are not impaired. Such other functional components include, for example, various fillers, reinforcing materials, flame retardants, antioxidants, compatibilizers, coupling agents, lubricants, surface treatment agents, pigments, ultraviolet absorbers, antistatic agents. , Dispersant, neutralizer, foaming agent, cross-linking agent and the like. Further, a colorant may be added for coloring.
　本発明のベルトにおいては、上記配合を用いることにより、例えば、体積抵抗率を１０９～１０１１Ω・ｃｍの範囲内、表面抵抗率を１０６．５～１０８．５Ω／□の範囲内にて調整することができる。 In the belt of the present invention, by using the above formulation, for example, the volume resistivity is in the range of 10 9 to 10 11 Ω · cm, and the surface resistivity is in the range of 10 6.5 to 10 8.5 Ω / □. Can be adjusted within.
　本発明のベルトの厚さは、適用される部材等の形態に応じて適宜選定されるものであるが、好ましくは５０～２００μｍの範囲内である。また、その表面粗さとしては、好適には、ＪＩＳ　１０点平均粗さＲｚで１０μｍ以下、特に６μｍ以下、更には３μｍ以下とする。さらに、本発明のベルトの引張弾性率は、１０００ＭＰａ以上、特には１５００～３０００ＭＰａとすることが好ましい。 The thickness of the belt of the present invention is appropriately selected according to the form of the applied member or the like, but is preferably in the range of 50 to 200 μm. The surface roughness thereof is preferably 10 μm or less, particularly 6 μm or less, and further 3 μm or less in JIS 10-point average roughness Rz. Further, the tensile elastic modulus of the belt of the present invention is preferably 1000 MPa or more, particularly 1500 to 3000 MPa.
　また、本発明のベルトには、図１Ａ，１Ｂ中に一点鎖線で示すように、図２の画像形成装置における駆動ローラ１４などの駆動部材と接触する側の面に、該駆動部材に形成した嵌合部（図示せず）と嵌合する嵌合部を形成してもよい。本発明の導電性エンドレスベルトでは、このような嵌合部を設け、これを駆動部材に設けた嵌合部（図示せず）と嵌合させて走行させることにより、導電性エンドレスベルトの幅方向のずれを防止することができる。この場合、前記嵌合部は、特に制限されるものではないが、図１Ａ，１Ｂ中に示すように、ベルトの周方向（回転方向）に沿って連続する凸条とし、これを駆動ローラ等の駆動部材の周面に周方向に沿って形成した溝に嵌合させるようにすることが好ましい。 Further, as shown by the alternate long and short dash line in FIGS. 1A and 1B, the belt of the present invention is formed on the drive member on the surface of the image forming apparatus of FIG. 2 on the side in contact with the drive member such as the drive roller 14. A fitting portion that fits with the fitting portion (not shown) may be formed. In the conductive endless belt of the present invention, such a fitting portion is provided, and the fitting portion (not shown) provided on the drive member is fitted and run to run the conductive endless belt in the width direction of the conductive endless belt. It is possible to prevent the deviation of the belt. In this case, the fitting portion is not particularly limited, but as shown in FIGS. 1A and 1B, a continuous ridge is formed along the circumferential direction (rotational direction) of the belt, and this is a drive roller or the like. It is preferable that the drive member is fitted into a groove formed along the circumferential direction on the peripheral surface of the drive member.
　なお、図１Ａでは、１本の連続する凸条を嵌合部として設けた例を示したが、この嵌合部は多数の凸部をベルトの周方向（回転方向）に沿って一列に並べて突設してもよく、また嵌合部を２本以上設けたり（図１Ｂ）、ベルトの幅方向中央部に設けてもよい。更に、嵌合部として図１Ａ，１Ｂ中に示した凸条ではなく、ベルトの周方向（回転方向）に沿った溝を設け、これを前記駆動ローラ等の駆動部材の周面に周方向に沿って形成した凸条と嵌合させるようにしてもよい。 In addition, in FIG. 1A, an example in which one continuous convex strip is provided as a fitting portion is shown, but in this fitting portion, a large number of convex portions are arranged in a row along the circumferential direction (rotation direction) of the belt. It may be provided so as to project, two or more fitting portions may be provided (FIG. 1B), or may be provided at the central portion in the width direction of the belt. Further, instead of the ridges shown in FIGS. 1A and 1B as the fitting portion, a groove is provided along the circumferential direction (rotational direction) of the belt, and this is provided in the circumferential direction on the peripheral surface of the drive member such as the drive roller. It may be fitted with the ridges formed along the line.
　本発明のベルトは、上記基材樹脂およびカーボンブラック等を含む樹脂組成物の押出し成形により好適に製造することができ、具体的には例えば、二軸混練機により上記基材樹脂およびカーボンブラック等の各種配合成分を含む樹脂組成物を混練し、得られた混練物を環状ダイスを使って押出し成形することにより製造することができる。または、静電塗装等の粉体塗装法、ディップ法または遠心注型法も好適に採用することができる。特に、本発明のベルトを押出し成形により製造する場合、カーボンブラックおよびタルクが、押出し方向またはベルト内径を拡張する方向、すなわち、ベルト面に沿って配向しやすくなるものと考えられ、好ましい。 The belt of the present invention can be suitably produced by extrusion molding of a resin composition containing the above-mentioned base material resin and carbon black, and specifically, for example, the above-mentioned base material resin and carbon black by a twin-screw kneader. It can be produced by kneading a resin composition containing various compounding components of the above and extruding the obtained kneaded product using an annular die. Alternatively, a powder coating method such as electrostatic coating, a dip method or a centrifugal casting method can also be preferably adopted. In particular, when the belt of the present invention is manufactured by extrusion molding, it is considered that carbon black and talc are likely to be oriented in the extrusion direction or the direction in which the inner diameter of the belt is expanded, that is, along the belt surface, which is preferable.
　以下、本発明を、実施例を用いてより詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to examples.
　下記の表１に示す配合に従い、基材樹脂とカーボンブラックとを含む樹脂組成物を２軸混練機で混合分散して、ペレットを得た。このペレットを用いて、単軸押出機の先に円筒状のダイスを備えた成形機にて押出し成形することにより、内径２２０ｍｍ、厚さ１００μｍ、幅２５０ｍｍにて、エンドレス形状の転写ベルトを成形した。なお、表１中の配合量は、質量部を示す。 According to the formulation shown in Table 1 below, the resin composition containing the base resin and carbon black was mixed and dispersed with a twin-screw kneader to obtain pellets. Using these pellets, an endless shape transfer belt was formed with an inner diameter of 220 mm, a thickness of 100 μm, and a width of 250 mm by extrusion molding with a molding machine equipped with a cylindrical die at the tip of a single-screw extruder. .. The blending amount in Table 1 indicates a part by mass.
＜体積抵抗率の測定＞
　温度２３℃、相対湿度５０％にて、測定装置として、ハイレスタＵＰ　ＭＣＰ－ＨＴ４５０（三菱ケミカルアナリテック社製）にＵＲプローブを接続したものを用いて、電圧２５０Ｖにて測定を行い、周方向に３０ｍｍピッチで２０箇所測定した値の平均値として、体積抵抗率を求めた。結果は、桁数にて示した。 <Measurement of volume resistivity>
At a temperature of 23 ° C. and a relative humidity of 50%, a high-resta UP MCP-HT450 (manufactured by Mitsubishi Chemical Analytech Co., Ltd.) with a UR probe connected to it was used as a measuring device, and measurement was performed at a voltage of 250 V. The volume resistivity was determined as the average value of the values measured at 20 points at a pitch of 30 mm. The results are shown in digits.
＜表面抵抗率の測定＞
　温度２３℃、相対湿度５０％にて、測定装置として三菱化学社製の抵抗計ハイレスタ（プローブＵＲ－１００）を用いて、電圧２５０Ｖにて測定を行い、印加時間１０秒、周方向に３０ｍｍピッチで２０箇所測定した値の平均値として、ベルト周方向における表面抵抗率を求めた。結果は、桁数にて示した。 <Measurement of surface resistivity>
A measurement was performed at a temperature of 23 ° C. and a relative humidity of 50% using a resistivity meter Hiresta (probe UR-100) manufactured by Mitsubishi Chemical Corporation at a voltage of 250 V, an application time of 10 seconds, and a pitch of 30 mm in the circumferential direction. The surface resistivity in the circumferential direction of the belt was determined as the average value of the values measured at 20 points in. The results are shown in digits.
　これらの結果を、下記の表１中に併せて示す。また、下記の表２中に、使用した各カーボンブラックの平均粒子径およびＤＢＰ吸油量の値を示す。 These results are also shown in Table 1 below. In addition, the values of the average particle size and DBP oil absorption of each carbon black used are shown in Table 2 below.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
＊１）ＰＢＮ，帝人株式会社製、商品名ＴＱＢ－ＯＴ
＊２）ＰＢＮエラストマー，東洋紡株式会社製、商品名ペルプレンＥＮ－１６０００
＊３）ＰＢＴ，ポリプラスチックス株式会社製、商品名ジュラネックス８００ＦＰ
＊４）カルボジイミド化合物，日清紡ケミカル株式会社製　商品名カルボジライトＨＭＶ－８ＣＡ
＊５）カーボンブラック（１），デンカ株式会社製　商品名デンカブラック粒状（アセチレンブラック）
＊６）カーボンブラック（２），東海カーボン株式会社製　商品名トーカブラック＃５５００
＊７）カーボンブラック（３），三菱化学株式会社製　商品名三菱カーボンブラック＃３０３０Ｂ
＊８）カーボンブラック（４），三菱化学株式会社製　商品名三菱カーボンブラック＃３２３０Ｂ
＊９）カーボンブラック（５），三菱化学株式会社製　商品名三菱カーボンブラック＃３４００Ｂ
＊１０）カーボンブラック（６），ライオン株式会社製　商品名ＥＣＬ３００Ｊ
＊１１）タルク，浅田製粉株式会社製　商品名タルクＦＦＲ（平均粒子径（Ｄ５０）３．９μｍ） * 1) PBN, manufactured by Teijin Limited, trade name TQB-OT
* 2) PBN elastomer, manufactured by Toyobo Co., Ltd., trade name Perprene EN-16000
* 3) PBT, manufactured by Polyplastics Co., Ltd., trade name Juranex 800FP
* 4) Carbodiimide compound, manufactured by Nisshinbo Chemical Co., Ltd. Product name Carbodilite HMV-8CA
* 5) Carbon black (1), manufactured by Denka Co., Ltd. Product name Denka Black Granular (acetylene black)
* 6) Carbon black (2), manufactured by Tokai Carbon Co., Ltd. Product name Talker Black # 5500
* 7) Carbon black (3), manufactured by Mitsubishi Chemical Corporation Product name Mitsubishi Carbon Black # 3030B
* 8) Carbon black (4), manufactured by Mitsubishi Chemical Corporation Product name Mitsubishi Carbon Black # 3230B
* 9) Carbon black (5), manufactured by Mitsubishi Chemical Corporation Product name Mitsubishi Carbon Black # 3400B
* 10) Carbon black (6), manufactured by Lion Corporation Product name ECL300J
* 11) Talc, manufactured by Asada Flour Milling Co., Ltd. Product name Talc FFR (average particle size (D50) 3.9 μm)
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　上記表中に示すように、基材樹脂が熱可塑性ＰＢＴ樹脂、熱可塑性ＰＢＮ樹脂および熱可塑性ＰＢＮエラストマーからなるとともに、カーボンブラックの平均粒子径およびＤＢＰ吸油量を所定範囲とした各実施例のベルトにおいては、体積抵抗率を一定とした際に、ベルト周方向における表面抵抗率を低くすることができることが確かめられた。また、さらにタルクを配合することで、カーボンブラックの配合量を抑制しつつ上記効果が得られることも確かめられた。 As shown in the above table, the base resin is made of a thermoplastic PBT resin, a thermoplastic PBN resin, and a thermoplastic PBN elastomer, and the average particle size of carbon black and the DBP oil absorption amount are within a predetermined range. It was confirmed that the surface resistivity in the circumferential direction of the belt can be lowered when the volume resistivity is kept constant. It was also confirmed that the above effect can be obtained while suppressing the amount of carbon black blended by further blending talc.
１０　転写ベルト
１１ａ～１１ｄ　感光体ドラム
１２ａ～１２ｄ　現像部
１３　記録媒体
１４　駆動ローラまたはテンションローラ
１５　２次転写ローラ
１６　記録媒体送り装置
１７　定着装置 10 Transfer belts 11a to 11d Photoreceptor drums 12a to 12d Development unit 13 Recording medium 14 Drive roller or tension roller 15 Secondary transfer roller 16 Recording medium feeder 17 Fixing device

Claims (6)

  1. 　画像形成装置に用いられる無端ベルト状の導電性エンドレスベルトにおいて、
    　基材樹脂とカーボンブラックとを含有し、
    　前記基材樹脂が、熱可塑性ポリブチレンテレフタレート樹脂、熱可塑性ポリブチレンナフタレート樹脂および熱可塑性ポリブチレンナフタレートエラストマーからなるとともに、
    　前記カーボンブラックの、平均粒子径が１５ｎｍ以上３０ｎｍ以下であって、ＤＢＰ吸油量が１５０ｃｍ３／１００ｇ以上３００ｃｍ３／１００ｇ以下であることを特徴とする導電性エンドレスベルト。     In an endless belt-shaped conductive endless belt used in an image forming apparatus,
    Contains base resin and carbon black,
    The base resin is composed of a thermoplastic polybutylene terephthalate resin, a thermoplastic polybutylene naphthalate resin, and a thermoplastic polybutylene naphthalate elastomer.
    Wherein the carbon black, the average particle diameter is not more 15nm or 30nm or less, conductive endless belt, wherein the DBP oil absorption is less than 150 cm 3/100 g or more 300 cm 3/100 g.
  2. 　前記基材樹脂の全量に対し、前記熱可塑性ポリブチレンテレフタレート樹脂を３６質量％以上含有する請求項１記載の導電性エンドレスベルト。 The conductive endless belt according to claim 1, which contains 36% by mass or more of the thermoplastic polybutylene terephthalate resin with respect to the total amount of the base resin.
  3. 　前記熱可塑性ポリブチレンナフタレート樹脂と前記熱可塑性ポリブチレンテレフタレート樹脂との質量比率が、０．６４～１．５の範囲内である請求項１または２記載の導電性エンドレスベルト。 The conductive endless belt according to claim 1 or 2, wherein the mass ratio of the thermoplastic polybutylene naphthalate resin to the thermoplastic polybutylene terephthalate resin is in the range of 0.64 to 1.5.
  4. 　前記基材樹脂１００質量部に対し、前記カーボンブラックを５質量部以上２０質量部以下で含有する請求項１～３のうちいずれか一項記載の導電性エンドレスベルト。 The conductive endless belt according to any one of claims 1 to 3, which contains 5 parts by mass or more and 20 parts by mass or less of the carbon black with respect to 100 parts by mass of the base resin.
  5. 　前記基材樹脂１００質量部に対し、さらに、タルクを３質量部以上２０質量部以下で含有する請求項１～４のうちいずれか一項記載の導電性エンドレスベルト。 The conductive endless belt according to any one of claims 1 to 4, further containing 3 parts by mass or more and 20 parts by mass or less of talc with respect to 100 parts by mass of the base resin.
  6. 　転写ベルトである請求項１～５のうちいずれか一項記載の導電性エンドレスベルト。 The conductive endless belt according to any one of claims 1 to 5, which is a transfer belt.
PCT/JP2020/006605 2019-05-10 2020-02-19 Conductive endless belt WO2020230394A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024024662A1 (en) * 2022-07-25 2024-02-01 三菱ケミカル株式会社 Resin composition and molded object

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003005538A (en) * 2001-06-26 2003-01-08 Yuka Denshi Co Ltd Endless belt, belt for image forming device and image forming device
JP2008089981A (en) * 2006-10-02 2008-04-17 Bridgestone Corp Conductive endless belt
JP2008292842A (en) * 2007-05-25 2008-12-04 Bridgestone Corp Conductive endless belt
US20120237863A1 (en) * 2011-03-17 2012-09-20 Xerox Corporation Intermediate transfer member and composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003005538A (en) * 2001-06-26 2003-01-08 Yuka Denshi Co Ltd Endless belt, belt for image forming device and image forming device
JP2008089981A (en) * 2006-10-02 2008-04-17 Bridgestone Corp Conductive endless belt
JP2008292842A (en) * 2007-05-25 2008-12-04 Bridgestone Corp Conductive endless belt
US20120237863A1 (en) * 2011-03-17 2012-09-20 Xerox Corporation Intermediate transfer member and composition

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024024662A1 (en) * 2022-07-25 2024-02-01 三菱ケミカル株式会社 Resin composition and molded object

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