TW201402694A - Seamless belt - Google Patents

Seamless belt Download PDF

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TW201402694A
TW201402694A TW102121500A TW102121500A TW201402694A TW 201402694 A TW201402694 A TW 201402694A TW 102121500 A TW102121500 A TW 102121500A TW 102121500 A TW102121500 A TW 102121500A TW 201402694 A TW201402694 A TW 201402694A
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seamless belt
carbon nanotube
dispersed
polyimide resin
carbon nanotubes
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TW102121500A
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Chinese (zh)
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Sang-Kyun Kim
Sang-Min Song
Ki-Nam Kwak
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Kolon Inc
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1042Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1046Polyimides containing oxygen in the form of ether bonds in the main chain
    • C08G73/105Polyimides containing oxygen in the form of ether bonds in the main chain with oxygen only in the diamino moiety
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1067Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • C08G73/1071Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/02Elements
    • C08K3/04Carbon
    • C08K3/041Carbon nanotubes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D179/00Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03GELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
    • G03G15/00Apparatus for electrographic processes using a charge pattern
    • G03G15/14Apparatus for electrographic processes using a charge pattern for transferring a pattern to a second base
    • G03G15/16Apparatus 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
    • G03G15/1605Apparatus 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 using at least one intermediate support
    • G03G15/162Apparatus 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 using at least one intermediate support details of the the intermediate support, e.g. chemical composition
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/011Nanostructured additives

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
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  • Manufacturing & Machinery (AREA)
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  • Physics & Mathematics (AREA)
  • Nanotechnology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Electrostatic Charge, Transfer And Separation In Electrography (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)

Abstract

This invention relates to a seamless belt, including a single-layer substrate including a polyimide resin and carbon nanotubes dispersed in the polyimide resin, wherein the polyimide resin is obtained by imidizing an aromatic dianhydride and an aromatic diamine, and the aromatic diamine includes 40 ~ 100 mol% of 1,4-phenylenediamine (1,4-PDA) based on the total amount of the aromatic diamine, and the carbon nanotubes have a diameter of 5 ~ 20 nm and are contained in an amount of 0.1 ~ 2.0 parts by weight based on 100 parts by weight of the polyimide resin.

Description

無縫帶 Seamless belt

本發明係關於一種無縫帶,尤其係一種可用作影像形成裝置中間傳送帶的無縫帶。 The present invention relates to a seamless belt, and more particularly to a seamless belt that can be used as an intermediate conveyor belt for an image forming apparatus.

一般來說,傳送帶的用途很廣泛,例如電子機器、汽車和輸送機等使用旋轉軸、電動機的產業,傳送帶一直被使用為可以代替傳動裝置的主要構件。特別是使用在複印機、雷射印表機以及傳真機等電子機器上,功能是把形成的碳粉影像印製和轉印在複印紙和轉印紙上,這樣的傳送帶也可以作為中間轉印帶和輸送帶來使用。 In general, conveyor belts are used for a wide variety of applications, such as electronic machines, automobiles, and conveyors, which use rotating shafts and electric motors. Conveyor belts have been used as the main components that can replace the transmission. Especially in electronic machines such as copiers, laser printers and fax machines, the function is to print and transfer the formed toner image onto copy paper and transfer paper. Such a conveyor belt can also be used as an intermediate transfer belt. And conveyor belts are used.

傳送帶在運轉的過程中很容易產生靜電,所以傳送帶被要求具有抗靜電功能。由於半導體的特性具有抗靜電的功能,因此可以應用在電子機器的碳粉轉印上。 Conveyor belts are prone to static electricity during operation, so conveyor belts are required to have antistatic properties. Since the characteristics of the semiconductor have an antistatic function, it can be applied to toner transfer of an electronic machine.

一般傳送帶是管狀的,規格從直徑20mm到數米皆有。但是大部分的傳送帶,例如平皮帶或V-型帶等,其黏接處有接合點,因此該黏接處的表面並不平整,這樣接合點的表面特性就會和周邊其他部分不同。電子機器特別需要使用均勻平整的傳送帶,尤其是彩色雷射印表機,若其中間轉印帶的表面不平整,就可能會損傷感光鼓或是降低印刷畫面的品質。而且,若接合點稍有一點扭曲就會破壞管形傳送帶的直線性,從而使運轉產生錯誤。這種運轉錯誤可能會導致傳送帶從傳動輥上分離,使機器發生損傷。 Generally, the conveyor belt is tubular, and the specifications range from 20mm to several meters. However, most conveyor belts, such as flat belts or V-belts, have joints at the joints, so the surface of the joint is not flat, so that the surface characteristics of the joints are different from those of other parts. Electronic machines in particular require the use of evenly flat conveyor belts, especially color laser printers. If the surface of the intermediate transfer belt is not flat, it may damage the photosensitive drum or degrade the quality of the printed image. Moreover, if the joint is slightly twisted, the linearity of the tubular conveyor belt is broken, and the operation is erroneous. This misoperation may cause the conveyor to separate from the drive roller and cause damage to the machine.

因此若管形傳送帶沒有接合點,則可以使傳送帶的耐用性達到最大。同時,由於表面平整,所以在運轉過程中就會防止傳送帶或是與 傳送帶接觸的物件發生彈跳現象,而且可以確保傳送帶的直線性。 Therefore, if the tubular conveyor has no joint, the durability of the belt can be maximized. At the same time, because the surface is flat, it will prevent the conveyor belt or The object touched by the conveyor belt bounces and ensures the linearity of the conveyor belt.

特別是使用在印表機、複印機、複合機、傳真機等電子機器的定影帶、中間轉印帶等,都應該具有良好的抗污性、耐熱性、散熱性、彈性係數、抗靜電性、耐用性、防水性、防油性和防帶電的特性;同時為了能夠轉印碳粉,傳送帶應具有適當的表面電阻係數。在表面電阻率係數比過高或過低的情況下,傳送帶的物性如防止帶電特性、轉印性、影像特性、異形性和抗污性也會同時被降低,這樣就有可能出現印刷畫質不良的嚴重瑕疵。 In particular, fixing belts, intermediate transfer belts, etc., which are used in electronic equipment such as printers, copiers, laminating machines, and facsimile machines, should have good stain resistance, heat resistance, heat dissipation, elastic modulus, and antistatic properties. Durability, water resistance, oil repellency and anti-charge characteristics; and in order to be able to transfer toner, the conveyor belt should have an appropriate surface resistivity. In the case where the surface resistivity coefficient ratio is too high or too low, the physical properties of the conveyor belt such as the prevention of charging characteristics, transferability, image characteristics, irregularity and stain resistance are also simultaneously lowered, so that print quality may occur. Bad seriousness.

定影帶、中間轉印帶等傳送帶在製造過程中,使用的材料為聚碳酸酯、聚偏二氟乙烯、聚醯胺纖維、聚醯亞胺樹脂或橡膠,再使其與導電性添加劑混合、分離後完成製造過程。但是為了加速印刷,同時又要避免在運轉過程中出現色重疊或不符的問題,進而有傳送帶可反覆使用、可承受高強度的要求。而且,傳送帶也被要求具有難燃性,所以材質上最好使用聚醯亞胺樹脂。又,使用如碳黑的導電性添加劑時,一旦添加的量不合適就很難確保達到預期的導電性效果,而且還需添加大量的分散劑來確保表面電阻率的均勻度,這樣一來傳送帶的耐用性就會降低。 Conveyor belts such as fixing belts and intermediate transfer belts are made of polycarbonate, polyvinylidene fluoride, polyamide fibers, polyimide resin or rubber during the manufacturing process, and then mixed with conductive additives. The manufacturing process is completed after separation. However, in order to speed up the printing, at the same time, it is necessary to avoid the problem of color overlap or inconsistency during the operation, and thus the conveyor belt can be used repeatedly and can withstand high strength requirements. Moreover, the conveyor belt is also required to be flame retardant, so it is preferable to use a polyimide resin for the material. Moreover, when a conductive additive such as carbon black is used, it is difficult to ensure that the desired conductivity effect is achieved once the amount of addition is not appropriate, and a large amount of dispersant is added to ensure uniformity of surface resistivity, so that the conveyor belt The durability will be reduced.

以下係關於包含聚醯亞胺樹脂和導電性填充料的無縫帶習知技術,該技術一直延續著,並已為韓國專利第2011-0032917號揭露。該無縫帶含有聚醯亞胺和聚醯胺纖維樹脂,根據熱重分析法測量可知,當起始溫度達300度以上重量減少5%時,其表面電阻率為107~1013Ω/sq。在一個樣品上的任意10個位置進行測量,得出的表面電阻率最大值和最小值的差值被定義為表面電阻率偏差,依此該無縫帶的表面電阻率偏差在10以下。但是,所述無縫帶不容易調控碳奈米管的分散狀態,所以如果被當作中間轉印帶使用的話,存在著耐用性等方面的問題。 The following is a conventional technique for a seamless belt comprising a polyimide resin and a conductive filler, which has been continued and disclosed in Korean Patent No. 2011-0032917. The seamless belt contains a polyimine and a polyamide fiber resin. According to the thermogravimetric analysis, when the initial temperature reaches 300 degrees or more and the weight is reduced by 5%, the surface resistivity is 10 7 to 10 13 Ω / Sq. The measurement is performed at any 10 positions on a sample, and the difference between the maximum and minimum values of the surface resistivity is defined as the surface resistivity deviation, whereby the surface resistivity deviation of the seamless belt is 10 or less. However, the seamless belt does not easily regulate the dispersion state of the carbon nanotubes, so if it is used as an intermediate transfer belt, there are problems in durability and the like.

本發明希望研製出能提高耐用性,具備良好的表面電阻率均勻度的無縫帶。 The present invention contemplates the development of a seamless belt that improves durability and has good surface resistivity uniformity.

本發明較佳實施例所提及的無縫帶,包含單一層的聚醯亞胺樹脂,該聚醯亞胺樹脂中包含分散的碳奈米管,其中,該聚醯亞胺樹脂係由芳香族二酐及芳香族二胺經過醯亞胺化所得到。芳香族二胺包含占該芳香族二胺總量40~100莫耳%的1,4-苯二胺(1,4-PDA)。碳奈米管的直徑為5~20nm,其含量占100重量份聚醯亞胺樹脂的0.1~2.0重量份。 The seamless belt as mentioned in the preferred embodiment of the present invention comprises a single layer of a polyimide resin comprising a dispersed carbon nanotube in which the polyimine resin is aroma The dianhydride and the aromatic diamine are obtained by oxime imidization. The aromatic diamine contains 1,4-phenylenediamine (1,4-PDA) in an amount of 40 to 100 mol% based on the total amount of the aromatic diamine. The carbon nanotubes have a diameter of 5 to 20 nm and a content of 0.1 to 2.0 parts by weight based on 100 parts by weight of the polyimine resin.

根據以上實施例,該碳奈米管係先在溶劑中分散後再分散於該聚醯亞胺樹脂中,分散在溶劑中的碳奈米管其粒徑可為0.02~10μm。 According to the above embodiment, the carbon nanotubes are dispersed in the solvent and then dispersed in the polyimide resin, and the carbon nanotubes dispersed in the solvent may have a particle diameter of 0.02 to 10 μm.

根據以上實施例,芳香族二酐可為聯苯四羧酸二酐(BPDA)。 According to the above examples, the aromatic dianhydride may be biphenyltetracarboxylic dianhydride (BPDA).

根據以上實施例,芳香族二胺可以包含選自由1,3-苯二胺(1,3-PDA)、4,4'-亞甲基二苯胺(MDA)、4,4'-二氨基二苯醚(ODA)及4,4'-氧苯二胺(OPDA)所組成的組合中的一種以上。 According to the above examples, the aromatic diamine may comprise selected from the group consisting of 1,3-phenylenediamine (1,3-PDA), 4,4'-methylenediphenylamine (MDA), 4,4'-diaminodi One or more of a combination of phenyl ether (ODA) and 4,4'-oxyphenylenediamine (OPDA).

根據以上實施例,無縫帶的表面電阻率可為108~1013Ω/sq。 According to the above embodiment, the surface resistivity of the seamless belt may be from 10 8 to 10 13 Ω/sq.

根據以上實施例,無縫帶的表面電阻率偏差的常用對數值可為1.0以下。 According to the above embodiment, the common logarithmic value of the surface resistivity deviation of the seamless belt may be 1.0 or less.

根據以上實施例,無縫帶的拉伸彈性模量可大於4000MPa以上。 According to the above embodiment, the tensile elastic modulus of the seamless belt may be more than 4,000 MPa or more.

根據以上實施例,無縫帶的耐折強度可大於1000回以上。 According to the above embodiment, the seamless belt may have a folding strength of more than 1000 times.

本發明的無縫帶具有表面電阻率的均勻性,提高了耐用性,尤其是對可靠性有要求的中間傳輸帶,可表現出其恰當的物性。 The seamless belt of the present invention has uniformity of surface resistivity and improves durability, and particularly an intermediate belt which requires reliability, can exhibit its proper physical properties.

第1圖是利用穿透式電子顯微鏡(TEM)測量本發明碳奈米管的直徑的示意圖;第2圖是本發明實施例1之碳奈米管的分散液其粒性測定結果的示意圖;以及第3圖是本發明比較例6之碳奈米管的分散液其粒性測定結果的示意 圖。 1 is a schematic view showing measurement of the diameter of the carbon nanotube of the present invention by a transmission electron microscope (TEM); and FIG. 2 is a schematic view showing the result of measurement of the granularity of the dispersion of the carbon nanotube of the embodiment 1 of the present invention; And Fig. 3 is a schematic view showing the results of measurement of the granularity of the dispersion of the carbon nanotube of Comparative Example 6 of the present invention. Figure.

以下,為對本發明更詳細的說明。 Hereinafter, the present invention will be described in more detail.

本發明是關於無縫帶,其係以二酐和二胺先製造出聚醯胺酸溶液,於該溶液中分散碳奈米管後,再把此獲得具半導電延展性的聚醯胺酸溶液進行醯亞胺化所製得。 The present invention relates to a seamless belt which is prepared by first preparing a polyaminic acid solution with a dianhydride and a diamine. After dispersing the carbon nanotube in the solution, the semi-conductive ductile polyamic acid is obtained. The solution was prepared by hydrazine imidization.

上述無縫帶包含單一層的聚醯亞胺樹脂,以及分散於聚醯亞胺樹脂中碳奈米管。本發明是關於以下特徵的無縫帶,把芳香族二酐及芳香族二胺醯亞胺化可得到聚醯亞胺樹脂。芳香族二胺包含占總量40~100莫耳%的1,4-苯二胺(1,4-PDA)。該碳奈米管的直徑是5~20nm,其含量占100重量份聚醯亞胺樹脂的0.1~2.0重量份。 The above seamless belt comprises a single layer of a polyimide resin and a carbon nanotube dispersed in the polyimide resin. The present invention relates to a seamless belt of the following characteristics, which is obtained by imidating an aromatic dianhydride and an aromatic diamine oxime to obtain a polyimide resin. The aromatic diamine contains 1,4-phenylenediamine (1,4-PDA) in a total amount of 40 to 100 mol%. The carbon nanotube has a diameter of 5 to 20 nm and a content of 0.1 to 2.0 parts by weight based on 100 parts by weight of the polyimine resin.

本發明中使用的用語「直徑」是指一條具有圓筒形的長條碳結構的碳奈米管的圓筒直徑。 The term "diameter" as used in the present invention means a cylinder diameter of a carbon nanotube having a cylindrical elongated carbon structure.

另外,本發明中使用的用語「粒徑」是指依據碳奈米管原來軸向的長度互相纏繞的傾向,和藉由凡得瓦力相互凝聚以集束形態存在的這種凝聚形態的大小。 Further, the term "particle diameter" as used in the present invention means a tendency to entangle each other in accordance with the length of the original axial direction of the carbon nanotubes, and a size of such agglomerated form in which the van der Waals force agglomerates in a bundle form.

歷來為了賦予影像形成裝置用之無縫帶具有傳導性,廣為人知的方法係以碳黑作為材料。 Conventionally, in order to impart conductivity to a seamless belt for an image forming apparatus, a well-known method uses carbon black as a material.

但是為使具絕緣性的聚醯亞胺樹脂,能夠具有傳導性,而使碳粉能夠帶電的應用,必須添加10重量%以上的碳黑。如此大量添加碳黑,會有降低聚醯亞胺樹脂既有的良好機械物性的問題。 However, in order to make the insulating polyimide resin capable of conductivity, it is necessary to add 10% by weight or more of carbon black to the application in which the carbon powder can be charged. The addition of carbon black in such a large amount has a problem of lowering the good mechanical properties of the polyimide resin.

本發明的傳導性材料使用碳奈米管,而碳奈米管於Sumio Iijima[S.Iijima,Nature Vol.354,P.56(1991年)]最初發現後,研究人員便積極對此進行研究。碳奈米管有既存材料所不具備的高彈性係數1.0~1.8TPa,並可承受真空狀態中2800℃的高溫,且熱傳導係數接近鑽石的兩倍,以及比銅高1000倍的導電能力等潛在物性。因此在奈米級的電子裝置、電 子元件、奈米感測器、光電子元件及高效能複合材料等所有領域中,被應用的可能性非常高。碳奈米管可看作石墨片中原子捲起來的圓筒狀,其直徑屬奈米級的極小物質。 The conductive material of the present invention uses a carbon nanotube, and after the initial discovery of the carbon nanotube in Sumio Iijima [S. Iijima, Nature Vol. 354, P. 56 (1991), the researchers actively studied this. . Carbon nanotubes have a high modulus of elasticity of 1.0 to 1.8 TPa, which is not possessed by existing materials, and can withstand a high temperature of 2800 ° C in a vacuum state, and the heat transfer coefficient is nearly twice that of diamonds, and the conductivity is 1000 times higher than that of copper. Physical properties. Therefore, in the nano-level electronic devices, electricity Sub-components, nanosensors, optoelectronic components, and high-performance composite materials are highly likely to be used in all fields. The carbon nanotube can be regarded as a cylindrical shape in which the atom in the graphite sheet is rolled up, and its diameter is a very small substance of a nanometer order.

碳奈米管根據構造可分為一層的單壁碳奈米管和多層呈同心圓狀的多壁碳奈米管。單壁碳奈米管的直徑是1.0nm,而根據壁的數量,多壁碳奈米管的直徑可達到2~100nm。單壁碳奈米管傳導性非常良好,但多壁碳奈米管的直徑越大傳導性卻越弱。 According to the structure, the carbon nanotubes can be divided into one layer of single-walled carbon nanotubes and a plurality of layers of concentric circular multi-walled carbon nanotubes. The diameter of the single-walled carbon nanotubes is 1.0 nm, and depending on the number of walls, the diameter of the multi-walled carbon nanotubes can reach 2 to 100 nm. Single-walled carbon nanotubes are very conductive, but the larger the diameter of a multi-walled carbon nanotube, the weaker the conductivity.

本發明碳奈米管的直徑可以是5~20nm,直徑若小於5nm時,傳導性非常高,因此為了滿足用於影像形成裝置的半導電性無縫帶的電性要求,應該添加很少的量,所以操作變難,也很難調節無縫帶的表面電阻率偏差。另外,使用直徑超過20nm的碳奈米管時,碳奈米管自身的傳導性減弱,因此為了滿足用於影像形成裝置中無縫帶的電性要求,應添加大量的碳奈米管,這比使用碳黑更不好。碳奈米管的直徑可藉由穿透式電子顯微鏡(TEM)進行量測,其結果如第1圖所示。 The carbon nanotube of the present invention may have a diameter of 5 to 20 nm, and if the diameter is less than 5 nm, the conductivity is very high, so in order to satisfy the electrical requirements of the semiconductive seamless belt used for the image forming apparatus, few additions should be added. The amount is so difficult to operate, and it is difficult to adjust the surface resistivity deviation of the seamless belt. In addition, when a carbon nanotube having a diameter of more than 20 nm is used, the conductivity of the carbon nanotube itself is weakened, so in order to satisfy the electrical requirements for the seamless belt used in the image forming apparatus, a large amount of carbon nanotubes should be added. It's worse than using carbon black. The diameter of the carbon nanotubes can be measured by a transmission electron microscope (TEM), and the results are shown in Fig. 1.

依照本發明實施例的無縫帶,於製造初期並非使用粉末狀的碳奈米管,為了使其均勻分佈在聚醯亞胺樹脂,可以先把碳奈米管添加在溶劑中以分散狀態使用。此時可使用甲醇、乙醇、丙醇、異丙醇、丁醇、乙二醇、N,N-二甲基甲醯胺、二甲基乙醯胺、丁酮、乙酸乙酯、乙酸丁酯、丙酮、甲苯等有機溶劑作為溶劑。尤其最好選擇使用N,N-二甲基甲醯胺、二甲基乙醯胺、N-甲基吡咯烷酮等非質子二極性溶劑。此時,溶劑中分散的碳奈米管的粒徑可以是0.02~10μm,較佳者可為0.1~8μm。加入溶劑中的碳奈米管通過銑床和超聲波分散,分散後粒徑會變小。加入溶劑中的碳奈米管在分散前初期測量粒徑時,因為碳奈米管原本不是一個一個地存在,而是集束存在,所以初期粒徑在1000μm左右;越反覆分散,碳奈米管受到外力,粒徑將變得越小。如果溶劑中分散的碳奈米管的粒徑超過10μm,溶劑中分散的碳奈米管粒子凝聚的團塊越大,會使上述樹脂的凝聚力減弱,而從有溶劑中分散的碳奈米管粒子的位置開始發生破裂,這會造成耐折強度的弱化。此時溶劑也可以是二甲基甲醯胺(DMF)。 In the seamless belt according to the embodiment of the present invention, a powdery carbon nanotube is not used in the initial stage of manufacture, and in order to uniformly distribute the polyimine resin, the carbon nanotube may be first added to a solvent to be used in a dispersed state. . At this time, methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol, N,N-dimethylformamide, dimethylacetamide, methyl ethyl ketone, ethyl acetate, butyl acetate can be used. An organic solvent such as acetone or toluene is used as a solvent. In particular, it is preferred to use an aprotic dipolar solvent such as N,N-dimethylformamide, dimethylacetamide or N-methylpyrrolidone. At this time, the particle diameter of the carbon nanotubes dispersed in the solvent may be 0.02 to 10 μm, preferably 0.1 to 8 μm. The carbon nanotubes added to the solvent are dispersed by a milling machine and ultrasonic waves, and the particle size becomes smaller after dispersion. When the carbon nanotubes added to the solvent are initially measured before the dispersion, since the carbon nanotubes are not originally present one by one, but the bundles exist, the initial particle diameter is about 1000 μm; the more repeated dispersion, the carbon nanotubes The external force will cause the particle size to become smaller. If the particle diameter of the carbon nanotubes dispersed in the solvent exceeds 10 μm, the larger the agglomerates of the dispersed carbon nanotube particles in the solvent, the weaker the cohesive force of the above resin, and the carbon nanotubes dispersed from the solvent. The position of the particles begins to rupture, which causes a weakening of the folding strength. The solvent may also be dimethylformamide (DMF) at this time.

另外,上述碳奈米管的含量可以占100重量份聚醯亞胺樹脂的0.1~2.0重量份。如果碳奈米管的含量不滿0.1重量份,電阻比要求值高;如果碳奈米管的含量超過2.0重量份,會有電阻比要求值低的問題。即,由於影像形成裝置使用的無縫帶有將碳粉從筒裏輸送到紙張的功能,所以其電阻範圍應該在半導電範圍之內。但由於聚醯亞胺樹脂自身的絕緣性,即不導電,加入如碳奈米管的傳導性物質,可使其具備半導電的電阻範圍,但是碳奈米管的含量最好是適當。 Further, the content of the carbon nanotubes may be 0.1 to 2.0 parts by weight based on 100 parts by weight of the polyimide resin. If the content of the carbon nanotubes is less than 0.1 parts by weight, the electric resistance ratio is higher than the required value; if the content of the carbon nanotubes exceeds 2.0 parts by weight, there is a problem that the electrical resistance is lower than the required value. That is, since the image forming apparatus uses a seamless function of transporting toner from the drum to the paper, its resistance range should be within the semi-conductive range. However, since the polyimide resin itself is insulative, that is, it is not electrically conductive, a conductive material such as a carbon nanotube can be added to have a semiconducting resistance range, but the content of the carbon nanotube is preferably appropriate.

根據本發明的無縫帶,聚醯亞胺樹脂是把聯苯四羧酸二酐和芳香族二胺經醯亞胺化得到的,上述芳香族二胺可包含占總量40~100莫耳%的1,4'-苯二胺(1,4-PDA)。 According to the seamless belt of the present invention, the polyimine resin is obtained by imidating biphenyltetracarboxylic dianhydride and aromatic diamine, and the above aromatic diamine may comprise 40 to 100 moles in total. % of 1,4'-phenylenediamine (1,4-PDA).

聚醯亞胺樹脂製造時使用二酐中的聯苯四羧酸二酐和二胺中的1,4'-苯二胺來聚合聚醯亞胺,能製造出剛硬且彈性良好的聚醯亞胺樹脂,以得到耐用性良好的無縫帶。此處的1,4'-苯二胺具有二胺中最短又剛硬的構造,使用占二胺總量40莫耳%以上的該成分,可製造出的具有高拉伸彈性係數的無縫帶。另一方面,除了二胺中的1,4'-苯二胺,如果使用60莫耳%以上的其它芳香族二胺,拉伸彈性係數會變低,長時間印刷時無縫帶會拉長;因此不能長久使用,降低了耐用性。 When a polyimine resin is produced by using a biphenyltetracarboxylic dianhydride in a dianhydride and 1,4'-phenylenediamine in a diamine to polymerize a polyimide, a rigid and elastic polycondensate can be produced. Imine resin for a seamless belt with good durability. Here, the 1,4'-phenylenediamine has the shortest and hardest structure of the diamine, and the composition having a high tensile modulus can be produced by using the component in an amount of more than 40 mol% based on the total amount of the diamine. band. On the other hand, in addition to the 1,4'-phenylenediamine in the diamine, if 60 mol% or more of other aromatic diamine is used, the tensile modulus of elasticity will become low, and the seamless belt will be elongated during long-time printing. Therefore, it cannot be used for a long time, which reduces durability.

另外,除了1,4-苯二胺之外,芳香族二胺可包含選自由1,3-苯二胺、4,4'-亞甲基二苯胺、4,4'-二氨基二苯醚及4,4'-氧苯二胺所組成的組合中的一種以上。上述的二酐可以用1,2,4,5-均苯四甲酸二酐(PMDA)、3,3',4,4'-聯苯四羧酸二酐(BPDA)、4,4'-二苯醚四甲酸二酐(ODPA)、4,4-(六氟異丙烯)二酞酸酐等,最好使用3,3',4,4'-聯苯四羧酸二酐(BPDA)。通常二胺和二酐使用同樣的量。尤其使用聯苯四羧酸二酐做為二酐時,拉伸彈性係數和耐折性比使用其他二酐表現得更良好。 Further, in addition to 1,4-phenylenediamine, the aromatic diamine may be selected from the group consisting of 1,3-phenylenediamine, 4,4'-methylenediphenylamine, 4,4'-diaminodiphenyl ether. And one or more of the combinations of 4,4'-oxyphenylenediamine. The above dianhydride can be used with 1,2,4,5- pyromellitic dianhydride (PMDA), 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA), 4,4'- Diphenyl ether tetracarboxylic acid dianhydride (ODPA), 4,4-(hexafluoroisopropene) dicarboxylic anhydride, etc., preferably 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA). Usually the same amount is used for the diamine and the dianhydride. In particular, when biphenyltetracarboxylic dianhydride is used as the dianhydride, the tensile modulus of elasticity and the folding endurance are better than those of other dianhydrides.

本發明可依據聚合條件和二酐成分及二胺成分的種類,調節聚醯亞胺樹脂的分子量,但最好根據二酐成分和二胺成分的莫耳比進行控制。具體而言,二酐/二胺的成分比例最好控制在100/100~90,或者100~90/100的範圍。但如果比例過量,樹脂的分子量下降,將造成無縫帶的 機械強度降低,引起半導電聚醯胺酸中分散的傳導性材料再凝聚,擴大所形成無縫帶的表面電阻率不均勻。 In the present invention, the molecular weight of the polyimine resin can be adjusted depending on the polymerization conditions and the type of the dianhydride component and the diamine component, but it is preferably controlled according to the molar ratio of the dianhydride component and the diamine component. Specifically, the component ratio of the dianhydride/diamine is preferably controlled in the range of 100/100 to 90 or 100 to 90/100. However, if the ratio is excessive, the molecular weight of the resin will decrease, which will result in a seamless belt. The mechanical strength is lowered, causing re-agglomeration of the conductive material dispersed in the semi-conductive polylysine, and the surface resistivity of the formed seamless belt is not uniform.

聚合本發明聚醯亞胺樹脂時使用的溶劑,可以將N-甲基-2-吡咯啶酮、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺、N-甲基己內醯胺等醯胺類極性溶劑單獨或兩種以上混合使用。 The solvent used in the polymerization of the polyimine resin of the present invention may be N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N- A guanamine-based polar solvent such as methyl caprolactam is used alone or in combination of two or more.

另外,無縫帶最好無縫地製造,其製造方法沒有特定的限制。例如本發明在圓筒形模具的表面以塗佈器塗上溶液狀的聚醯亞胺樹脂後,經過熱處理製造出無縫帶。上述熱處理係階段性的達到50~400℃,首先在50~100℃下進行10~120分鐘的預焙,把表面上殘存的溶劑及水分一次去除。之後維持每分鐘2~10℃的升溫速度,到350~400℃最終硬化完全去除表面上存在的溶劑及水分,進行醯亞胺化完成,同時製造出固化的無縫帶。 Further, the seamless belt is preferably manufactured seamlessly, and the manufacturing method thereof is not particularly limited. For example, in the present invention, after the solution is coated with a solution-like polyimide resin on the surface of a cylindrical mold, a seamless belt is produced by heat treatment. The heat treatment is carried out at a temperature of 50 to 400 ° C, and is first pre-baked at 50 to 100 ° C for 10 to 120 minutes to remove the solvent and moisture remaining on the surface. After that, the temperature rise rate of 2~10 °C per minute is maintained, and the final hardening at 350-400 °C completely removes the solvent and moisture present on the surface, and the hydrazine imidization is completed, and a cured seamless belt is produced.

無縫帶製造時以改善它的熱傳導性為目的。如果無縫帶厚度過薄,會發生無縫帶的強度大幅降低的現象,印刷過程中隨著反復的旋轉應力,無縫帶會出現裂痕或者發生扭曲現象。無縫帶的適當厚度是30~300μm。 The seamless belt is manufactured to improve its thermal conductivity. If the thickness of the seamless belt is too thin, the strength of the seamless belt may be greatly reduced. During the printing process, the seamless belt may be cracked or twisted due to repeated rotational stress. The appropriate thickness of the seamless belt is 30 to 300 μm.

本發明的無縫帶可以提供的表面電阻率為108~1013Ω/sq,且在無縫帶的任意區域上具有偏差小於1.0以下的均勻表面電阻率,其拉伸彈性模量大於4000MPa以上,耐折強度則大於1000回以上,因此係一機械性良好的無縫帶,可以作為具有耐用性的中間轉印帶。 The seamless belt of the present invention can provide a surface resistivity of 10 8 to 10 13 Ω/sq and a uniform surface resistivity with a deviation of less than 1.0 or less in any region of the seamless belt, and a tensile modulus of elasticity of more than 4000 MPa. As described above, the folding strength is more than 1000 times or more, so that it is a mechanically good seamless belt and can be used as an intermediate transfer belt having durability.

以下本發明實施例的詳細說明如下,但本發明不限於以下實施例。 The following detailed description of the embodiments of the present invention is as follows, but the present invention is not limited to the following embodiments.

實施例1 Example 1

根據表1所提及的成分,以下述的方法製造無縫帶。 According to the ingredients mentioned in Table 1, a seamless belt was produced in the following manner.

在機械攪拌機、回流式冷卻機以及氮氣進氣口所安裝的2L雙重外殼反應器中投入1460g的二甲基甲醯胺(DMF)。溫度調至30℃並在氮氣的環境中放入67.7g的4,4'-二氨基二苯醚(ODA)和24.4g的1,4'-苯二胺(PDA)作為二胺。攪拌大約30分鐘確認完全溶解後,投入165.7g的3,3',4,4'- 聯苯四羧酸二酐(BPDA)。投入後維持溫度的同時攪拌3小時。之後把占聚醯亞胺樹酯0.1重量份的碳奈米管於溶液中經分散處理後混入該聚醯胺酸溶液中。所使用的碳奈米管其直徑為5nm,分散液中碳奈米管的最小粒徑為0.2μm,最大粒徑為6μm。分散液中碳奈米管的粒性測定結果如第2圖。 1460 g of dimethylformamide (DMF) was charged in a 2 L double-shell reactor equipped with a mechanical stirrer, a reflux cooler, and a nitrogen gas inlet. The temperature was adjusted to 30 ° C and 67.7 g of 4,4'-diaminodiphenyl ether (ODA) and 24.4 g of 1,4'-phenylenediamine (PDA) were placed as a diamine under a nitrogen atmosphere. After stirring for about 30 minutes to confirm complete dissolution, put 165.7 g of 3,3', 4, 4'- Biphenyltetracarboxylic dianhydride (BPDA). After the input, the temperature was maintained while stirring for 3 hours. Thereafter, 0.1 part by weight of the carbon nanotubes of the polyamido resin was dispersed in the solution and mixed into the polyamic acid solution. The carbon nanotube used had a diameter of 5 nm, and the carbon nanotubes in the dispersion had a minimum particle diameter of 0.2 μm and a maximum particle diameter of 6 μm. The results of the measurement of the granularity of the carbon nanotubes in the dispersion are shown in Fig. 2.

前述製造出具半導電性的聚醯胺酸是均勻狀態的黑色溶液,黏度為200泊。 The above-mentioned semi-conductive polylysine was a black solution in a uniform state and had a viscosity of 200 poise.

在鍍鉻SUS 304材質、直徑330mm、厚度5mm、寬度500mm的無接頭成型金屬模具上,噴上離型劑(KAPIA,韓國)後在旋轉成型器上旋轉,把上述製備的半導電性聚醯胺酸溶液透過塗佈器均勻塗佈。之後在乾燥烘箱中放入上述成型金屬模具以10℃/分的速度升溫,在100℃、200℃、300℃下各定置30分鐘。醯亞胺化反應完成的同時完全去除溶劑和水分,冷卻後從SUS傳送帶取得聚醯亞胺薄層,製造出厚度為65μm的無縫帶,截斷無縫帶的兩端形成300mm的寬度。 On a jointless molding die made of chrome-plated SUS 304, 330 mm in diameter, 5 mm in thickness and 500 mm in width, sprayed with a release agent (KAPIA, Korea) and rotated on a rotary former to prepare the semiconductive polyamine prepared above. The acid solution is uniformly coated through the applicator. Thereafter, the above-mentioned molding metal mold was placed in a drying oven at a rate of 10 ° C /min, and each was set at 100 ° C, 200 ° C, and 300 ° C for 30 minutes. When the hydrazine imidization reaction was completed, the solvent and moisture were completely removed, and after cooling, a thin layer of polyimide was obtained from a SUS belt to produce a seamless belt having a thickness of 65 μm, and the ends of the cut-off seamless belt were formed to have a width of 300 mm.

實施例2 Example 2

在機械攪拌機、回流式冷卻機以及氮氣進氣口所安裝的2L雙重外殼反應器中投入1290g二甲基甲醯胺(DMF)。溫度調至30℃並在氮氣的環境中放入61.0g的1,4'-苯二胺(PDA)作為二胺。攪拌大約30分鐘確認完全溶解後,投入165.7g的3,3',4,4'-聯苯四羧酸二酐(BPDA)。投入後維持溫度的同時攪拌3小時。之後把占聚醯亞胺樹酯2重量份的碳奈米管於溶液中經分散處理後混入該聚醯胺酸溶液中。所使用的碳奈米管其直徑為20nm的碳奈米管,分散液中碳奈米管的最小粒徑為100nm(0.1μm),最大粒徑為7μm。 In a 2 L double-shell reactor equipped with a mechanical stirrer, a reflux chiller, and a nitrogen gas inlet, 1290 g of dimethylformamide (DMF) was charged. The temperature was adjusted to 30 ° C and 61.0 g of 1,4'-phenylenediamine (PDA) was placed as a diamine under a nitrogen atmosphere. After stirring for about 30 minutes to confirm complete dissolution, 165.7 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) was charged. After the input, the temperature was maintained while stirring for 3 hours. Thereafter, 2 parts by weight of the carbon nanotubes of the polyamidene resin were dispersed in the solution and mixed into the polyaminic acid solution. The carbon nanotube used was a carbon nanotube having a diameter of 20 nm, and the carbon nanotube in the dispersion had a minimum particle diameter of 100 nm (0.1 μm) and a maximum particle diameter of 7 μm.

將製造出的半導電性聚醯胺酸,以與實施例1中一樣的方法得到無縫帶。 The semiconductive polyphthalic acid to be produced was obtained in the same manner as in Example 1 to obtain a seamless belt.

比較例1 Comparative example 1

在機械攪拌機、回流式冷卻機以及氮氣進氣口所安裝的2L雙重外殼反應器中投入1490g二甲基甲醯胺(DMF)。溫度調至30℃並在氮氣的環境中放入79.0g的4,4'-二氨基二苯醚(ODA)和18.3g的1,4'-苯二胺(PDA) 作為二胺。攪拌大約30分鐘確認完全溶解後,投入165.7g的3,3',4,4'-聯苯四羧酸二酐(BPDA)。投入後維持溫度的同時攪拌3小時。之後把占聚醯亞胺樹酯0.5重量份的碳奈米管於溶液中經分散處理後混入該聚醯胺酸溶液中。所使用的碳奈米管其直徑為20nm的碳奈米管,分散液中碳奈米管的最小粒徑為20nm(0.02μm),最大粒徑為3μm。 1490 g of dimethylformamide (DMF) was charged in a 2 L double-shell reactor equipped with a mechanical stirrer, a reflux chiller, and a nitrogen gas inlet. The temperature was adjusted to 30 ° C and 79.0 g of 4,4'-diaminodiphenyl ether (ODA) and 18.3 g of 1,4'-phenylenediamine (PDA) were placed in a nitrogen atmosphere. As a diamine. After stirring for about 30 minutes to confirm complete dissolution, 165.7 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) was charged. After the input, the temperature was maintained while stirring for 3 hours. Thereafter, 0.5 part by weight of the carbon nanotubes containing the polyamidamine resin were dispersed in the solution and mixed into the polyaminic acid solution. The carbon nanotube used was a carbon nanotube having a diameter of 20 nm, and the carbon nanotube in the dispersion had a minimum particle diameter of 20 nm (0.02 μm) and a maximum particle diameter of 3 μm.

將製造出的半導電性聚醯胺酸,以與實施例1中一樣的方法得到無縫帶。 The semiconductive polyphthalic acid to be produced was obtained in the same manner as in Example 1 to obtain a seamless belt.

比較例2 Comparative example 2

在機械攪拌機、回流式冷卻機以及氮氣進氣口所安裝的2L雙重外殼反應器中投入1460g二甲基甲醯胺(DMF)。溫度調至30℃並在氮氣的環境中放入67.7g的4,4'-二氨基二苯醚(ODA)和24.4g的1,4'-苯二胺(PDA)作為二胺。攪拌大約30分鐘確認完全溶解後,投入165.7g的3,3',4,4'-聯苯四羧酸二酐(BPDA)。投入後維持溫度的同時攪拌3小時。之後把占聚醯亞胺樹酯0.1重量份的碳奈米管於溶液中經分散處理後混入該聚醯胺酸溶液中。所使用的碳奈米管其直徑為2nm的碳奈米管,分散液中碳奈米管的最小粒徑為20nm(0.02μm),最大粒徑為3μm。 1460 g of dimethylformamide (DMF) was charged in a 2 L double-shell reactor equipped with a mechanical stirrer, a reflux cooler, and a nitrogen gas inlet. The temperature was adjusted to 30 ° C and 67.7 g of 4,4'-diaminodiphenyl ether (ODA) and 24.4 g of 1,4'-phenylenediamine (PDA) were placed as a diamine under a nitrogen atmosphere. After stirring for about 30 minutes to confirm complete dissolution, 165.7 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) was charged. After the input, the temperature was maintained while stirring for 3 hours. Thereafter, 0.1 part by weight of the carbon nanotubes of the polyamido resin was dispersed in the solution and mixed into the polyamic acid solution. The carbon nanotube used was a carbon nanotube having a diameter of 2 nm, and the carbon nanotube in the dispersion had a minimum particle diameter of 20 nm (0.02 μm) and a maximum particle diameter of 3 μm.

將製造出的半導電性聚醯胺酸,以與實施例1中一樣的方法得到無縫帶。 The semiconductive polyphthalic acid to be produced was obtained in the same manner as in Example 1 to obtain a seamless belt.

比較例3 Comparative example 3

在機械攪拌機、回流式冷卻機以及氮氣進氣口所安裝的2L雙重外殼反應器中投入1460g二甲基甲醯胺(DMF)。溫度調至30℃並在氮氣的環境中放入67.7g的4,4'-二氨基二苯醚(ODA)和24.4g的1,4'-苯二胺(PDA)作為二胺。攪拌大約30分鐘確認完全溶解後,投入165.7g的3,3',4,4'-聯苯四羧酸二酐(BPDA)。投入後維持溫度的同時攪拌3小時。之後把占聚醯亞胺樹酯2重量份的碳奈米管於溶液中經分散處理後混入該聚醯胺酸溶液中。所使用的碳奈米管其直徑為30nm的碳奈米管,分散液中碳奈米管的最小粒徑為150nm(0.15μm),最大粒徑為10μm。 1460 g of dimethylformamide (DMF) was charged in a 2 L double-shell reactor equipped with a mechanical stirrer, a reflux cooler, and a nitrogen gas inlet. The temperature was adjusted to 30 ° C and 67.7 g of 4,4'-diaminodiphenyl ether (ODA) and 24.4 g of 1,4'-phenylenediamine (PDA) were placed as a diamine under a nitrogen atmosphere. After stirring for about 30 minutes to confirm complete dissolution, 165.7 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) was charged. After the input, the temperature was maintained while stirring for 3 hours. Thereafter, 2 parts by weight of the carbon nanotubes of the polyamidene resin were dispersed in the solution and mixed into the polyaminic acid solution. The carbon nanotube used was a carbon nanotube having a diameter of 30 nm, and the carbon nanotube in the dispersion had a minimum particle diameter of 150 nm (0.15 μm) and a maximum particle diameter of 10 μm.

將製造出的半導電性聚醯胺酸,以與實施例1中一樣的方法得到無縫帶。 The semiconductive polyphthalic acid to be produced was obtained in the same manner as in Example 1 to obtain a seamless belt.

比較例4 Comparative example 4

在機械攪拌機、回流式冷卻機以及氮氣進氣口所安裝的2L雙重外殼反應器中投入1460g二甲基甲醯胺(DMF)。溫度調至30℃並在氮氣的環境中放入67.7g的4,4'-二氨基二苯醚(ODA)和24.4g的1,4'-苯二胺(PDA)作為二胺。攪拌大約30分鐘確認完全溶解後,投入165.7g的3,3',4,4'-聯苯四羧酸二酐(BPDA)。投入後維持溫度的同時攪拌3小時。之後把占聚醯亞胺樹酯0.05重量份的碳奈米管於溶液中經分散處理後混入該聚醯胺酸溶液中。所使用的碳奈米管其直徑為20nm的碳奈米管,分散液中碳奈米管的最小粒徑為100nm(0.1μm),最大粒徑為5μm。 1460 g of dimethylformamide (DMF) was charged in a 2 L double-shell reactor equipped with a mechanical stirrer, a reflux cooler, and a nitrogen gas inlet. The temperature was adjusted to 30 ° C and 67.7 g of 4,4'-diaminodiphenyl ether (ODA) and 24.4 g of 1,4'-phenylenediamine (PDA) were placed as a diamine under a nitrogen atmosphere. After stirring for about 30 minutes to confirm complete dissolution, 165.7 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) was charged. After the input, the temperature was maintained while stirring for 3 hours. Thereafter, 0.05 part by weight of the carbon nanotubes of the polyamidene resin were dispersed in the solution and mixed into the polyaminic acid solution. The carbon nanotube used was a carbon nanotube having a diameter of 20 nm, and the carbon nanotube in the dispersion had a minimum particle diameter of 100 nm (0.1 μm) and a maximum particle diameter of 5 μm.

將製造出的半導電性聚醯胺酸,以與實施例1中一樣的方法得到無縫帶。 The semiconductive polyphthalic acid to be produced was obtained in the same manner as in Example 1 to obtain a seamless belt.

比較例5 Comparative Example 5

在機械攪拌機、回流式冷卻機以及氮氣進氣口所安裝的2L雙重外殼反應器中投入1460g二甲基甲醯胺(DMF)。溫度調至30℃並在氮氣的環境中放入67.7g的4,4'-二氨基二苯醚(ODA)和24.4g的1,4'-苯二胺(PDA)作為二胺。攪拌大約30分鐘確認完全溶解後,投入165.7g的3,3',4,4'-聯苯四羧酸二酐(BPDA)。投入後維持溫度的同時攪拌3小時。之後把占聚醯亞胺樹酯2.5重量份的碳奈米管於溶液中經分散處理後混入該聚醯胺酸溶液中。所使用的碳奈米管其直徑為20nm的碳奈米管,分散液中碳奈米管的最小粒徑為130nm(0.13μm),最大粒徑為8μm。 1460 g of dimethylformamide (DMF) was charged in a 2 L double-shell reactor equipped with a mechanical stirrer, a reflux cooler, and a nitrogen gas inlet. The temperature was adjusted to 30 ° C and 67.7 g of 4,4'-diaminodiphenyl ether (ODA) and 24.4 g of 1,4'-phenylenediamine (PDA) were placed as a diamine under a nitrogen atmosphere. After stirring for about 30 minutes to confirm complete dissolution, 165.7 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) was charged. After the input, the temperature was maintained while stirring for 3 hours. Thereafter, 2.5 parts by weight of the carbon nanotubes of the polyamido resin were dispersed in the solution and mixed into the polyamine solution. The carbon nanotube used was a carbon nanotube having a diameter of 20 nm, and the carbon nanotube in the dispersion had a minimum particle diameter of 130 nm (0.13 μm) and a maximum particle diameter of 8 μm.

將製造出的半導電性聚醯胺酸,以與實施例1中一樣的方法得到無縫帶。 The semiconductive polyphthalic acid to be produced was obtained in the same manner as in Example 1 to obtain a seamless belt.

比較例6 Comparative Example 6

在機械攪拌機、回流式冷卻機以及氮氣進氣口所安裝的2L雙重外殼反應器中投入1460g二甲基甲醯胺(DMF)。溫度調至30℃並在氮氣 的環境中放入67.7g的4,4'-二氨基二苯醚(ODA)和24.4g的1,4'-苯二胺(PDA)作為二胺。攪拌大約30分鐘確認完全溶解後,投入165.7g的3,3',4,4'-聯苯四羧酸二酐(BPDA)。投入後維持溫度的同時攪拌3小時。之後把占聚醯亞胺樹酯1.0重量份的碳奈米管於溶液中經分散處理後混入該聚醯胺酸溶液中。所使用的碳奈米管其直徑為20nm的碳奈米管,分散液中碳奈米管的最小粒徑為1.7μm,最大粒徑為63μm。分散液中碳奈米管的粒度測定結果如第3圖。 1460 g of dimethylformamide (DMF) was charged in a 2 L double-shell reactor equipped with a mechanical stirrer, a reflux cooler, and a nitrogen gas inlet. The temperature was adjusted to 30 ° C and the nitrogen was 67.7 g of 4,4'-diaminodiphenyl ether (ODA) and 24.4 g of 1,4'-phenylenediamine (PDA) were placed as a diamine. After stirring for about 30 minutes to confirm complete dissolution, 165.7 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (BPDA) was charged. After the input, the temperature was maintained while stirring for 3 hours. Thereafter, 1.0 part by weight of the carbon nanotubes of the polyamido resin was dispersed in the solution and mixed into the polyamic acid solution. The carbon nanotube used was a carbon nanotube having a diameter of 20 nm, and the carbon nanotube in the dispersion had a minimum particle diameter of 1.7 μm and a maximum particle diameter of 63 μm. The particle size measurement results of the carbon nanotubes in the dispersion are shown in Fig. 3.

將製造出的半導電性聚醯胺酸,以與實施例1中一樣的方法得到無縫帶。 The semiconductive polyphthalic acid to be produced was obtained in the same manner as in Example 1 to obtain a seamless belt.

測量以上述實施例及比較例的方法所製造之無縫帶的表面電阻率、表面電阻率偏差的常用對數值、碳奈米管的粒徑、拉伸彈性模量及耐折強度,結果如表2所示。 The surface resistivity, the common logarithm of the surface resistivity deviation, the particle diameter of the carbon nanotube, the tensile elastic modulus, and the folding strength of the seamless belt produced by the methods of the above Examples and Comparative Examples were measured. Table 2 shows.

(1)表面電阻率 (1) Surface resistivity

把上述實施例及比較例所製造的無縫帶在寬度方向上裁剪,以2維的形式將該薄層展開。在無縫帶的內、外面分別任選五個點。在選擇的十個點上,安裝三菱化學(Mitsubishi Chemical)公司的Hiresta UP高電阻率計UR-100探針,在100伏特的許可電壓下測量10秒鐘。取十個測量值的平均值。 The seamless belt manufactured in the above examples and comparative examples was cut in the width direction, and the thin layer was developed in a two-dimensional form. Choose five points inside and outside the seamless belt. At the selected ten points, Mitsubishi Chemical's Hiresta UP high resistivity meter UR-100 probe was installed and measured at a permit voltage of 100 volts for 10 seconds. Take the average of ten measured values.

(2)表面電阻率偏差的常用對數值 (2) Common logarithmic values of surface resistivity deviation

把上述實施例及比較例所製造的無縫帶在寬度方向上裁剪,以2維的形式將該薄層展開。在無縫帶的內、外面分別任選五個點。在選擇的十個點上,安裝三菱化學(Mitsubishi Chemical)公司的Hiresta UP高電阻率計UR-100探針,在100伏特的許可電壓下測量10秒鐘。取十個測量值中最大值和最小值的常用對數值再求其差。 The seamless belt manufactured in the above examples and comparative examples was cut in the width direction, and the thin layer was developed in a two-dimensional form. Choose five points inside and outside the seamless belt. At the selected ten points, Mitsubishi Chemical's Hiresta UP high resistivity meter UR-100 probe was installed and measured at a permit voltage of 100 volts for 10 seconds. Take the common logarithm of the maximum and minimum values of the ten measured values and then find the difference.

(3)溶劑中分散的碳奈米管的粒徑 (3) Particle size of carbon nanotubes dispersed in the solvent

把經過分散處理的碳奈米管分散液放到型號Microtrac S3500(Microtrac公司,美國)的粒徑分析儀上分析。以體積平均粒徑為基準。 The dispersed carbon nanotube dispersion was placed on a particle size analyzer of the model Microtrac S3500 (Microtrac, USA) for analysis. Based on the volume average particle diameter.

(4)拉伸彈性模量 (4) Tensile modulus of elasticity

於上述一種無縫帶取五張橫向15mm乘縱向100mm的樣品,放到Instron 3365SER試驗機上。根據ASTM D 882測量方法測量。 Five sheets of horizontal 15 mm by 100 mm longitudinal were taken from the above seamless belt and placed on an Instron 3365 SER test machine. Measured according to ASTM D 882 measurement method.

(5)耐折強度 (5) folding strength

於上述一種無縫帶取五張橫向15mm乘縱向100mm的樣品,放到MIT試驗機上。根據ASTM D 882測量方法測量。以R=2,彎曲角度135度,轉速175rpm的條件進行測量,量測反復彎曲的次數直到樣品斷裂。 Five sheets of horizontal 15 mm by 100 mm longitudinal were taken from the above seamless belt and placed on an MIT test machine. Measured according to ASTM D 882 measurement method. The measurement was carried out under conditions of R = 2, a bending angle of 135 degrees, and a rotational speed of 175 rpm, and the number of repeated bendings was measured until the sample was broken.

由以上表2的結果所示,根據本發明的實施例,於碳奈米管具有直徑為5~20nm、占0.1~2.0重量份、最小粒徑在0.02μm以上、最大粒徑在10μm以下,且聚醯亞胺樹脂含有占芳香族二胺總量40~100莫耳%的1,4-苯二胺,等特色下的無縫帶,其表面電阻率為108~1013Ω/sq,表面電阻率偏差小於1.0以下,拉伸彈性模量大於4000MPa以上,耐折強度大於1000回以上,因此實際上可以明顯提高耐用性。 As shown in the results of Table 2 above, according to an embodiment of the present invention, the carbon nanotube has a diameter of 5 to 20 nm, 0.1 to 2.0 parts by weight, a minimum particle diameter of 0.02 μm or more, and a maximum particle diameter of 10 μm or less. The polyimine resin contains 1,4-phenylenediamine in an amount of 40 to 100 mol% of the total amount of the aromatic diamine, and the surface resistivity is 10 8 to 10 13 Ω/sq. The surface resistivity deviation is less than 1.0, the tensile elastic modulus is more than 4,000 MPa, and the folding strength is more than 1000 rpm, so that the durability can be remarkably improved.

Claims (8)

一種無縫帶,包括:單一層的聚醯亞胺樹脂,該聚醯亞胺樹脂中包含分散的碳奈米管,其中,該聚醯亞胺樹脂係由芳香族二酐及芳香族二胺經過醯亞胺化所得到;該芳香族二胺包含占該芳香族二胺總量40~100莫耳%的1,4-苯二胺(1,4-PDA);該碳奈米管的直徑係5~20nm,其含量占100重量份聚醯亞胺樹脂的0.1~2.0重量份。 A seamless belt comprising: a single layer of a polyimide resin comprising a dispersed carbon nanotube, wherein the polyimide resin is composed of an aromatic dianhydride and an aromatic diamine Obtained by hydrazine imidation; the aromatic diamine comprises 1,4-phenylenediamine (1,4-PDA) in an amount of 40 to 100 mol% of the total amount of the aromatic diamine; The diameter is 5 to 20 nm, and the content thereof is 0.1 to 2.0 parts by weight based on 100 parts by weight of the polyimine resin. 依據申請專利範圍第1項所述的無縫帶,其中該碳奈米管係先在溶劑中分散後再加入該聚醯亞胺樹脂中,分散在該溶劑中的該碳奈米管其粒徑係0.02~10μm。 The seamless belt according to claim 1, wherein the carbon nanotube is first dispersed in a solvent and then added to the polyimide resin, and the carbon nanotube dispersed in the solvent is granulated. The diameter system is 0.02~10μm. 依據申請專利範圍第1項所述的無縫帶,其中該芳香族二酐係聯苯四羧酸二酐(BPDA)。 The seamless belt according to claim 1, wherein the aromatic dianhydride is biphenyltetracarboxylic dianhydride (BPDA). 依據申請專利範圍第1項所述的無縫帶,其中該芳香族二胺包含選自由1,3-苯二胺(1,3-PDA)、4,4'-亞甲基二苯胺(MDA)、4,4'-二氨基二苯醚(ODA)及4,4'-氧苯二胺(OPDA)所組成的組合中的一種以上。 The seamless belt according to claim 1, wherein the aromatic diamine comprises one selected from the group consisting of 1,3-phenylenediamine (1,3-PDA) and 4,4'-methylenediphenylamine (MDA). And one or more of a combination of 4,4'-diaminodiphenyl ether (ODA) and 4,4'-oxyphenylenediamine (OPDA). 依據申請專利範圍第1項所述的無縫帶,其中該無縫帶的表面電阻率係108~1013Ω/sq。 The seamless belt according to claim 1, wherein the seamless belt has a surface resistivity of 10 8 to 10 13 Ω/sq. 依據申請專利範圍第1項所述的無縫帶,其中該無縫帶的表面電阻率偏差的常用對數值係在1.0以下。 The seamless belt according to claim 1, wherein the common logarithmic value of the surface resistivity deviation of the seamless belt is 1.0 or less. 依據申請專利範圍第1項所述的無縫帶,其中該無縫帶的拉伸彈性模量係大於4000MPa以上。 The seamless belt according to claim 1, wherein the seamless belt has a tensile elastic modulus of more than 4,000 MPa. 依據申請專利範圍第1項所述的無縫帶,其中該無縫帶的耐折強度係大於1000回以上。 The seamless belt according to claim 1, wherein the seamless belt has a folding strength of more than 1000 times.
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