WO1999059034A1 - Materiau extrude par fusion se pretant a l'elaboration de la couche exterieure d'un rouleau fixateur de dispositif de formation d'image - Google Patents

Materiau extrude par fusion se pretant a l'elaboration de la couche exterieure d'un rouleau fixateur de dispositif de formation d'image Download PDF

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Publication number
WO1999059034A1
WO1999059034A1 PCT/JP1999/002193 JP9902193W WO9959034A1 WO 1999059034 A1 WO1999059034 A1 WO 1999059034A1 JP 9902193 W JP9902193 W JP 9902193W WO 9959034 A1 WO9959034 A1 WO 9959034A1
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WO
WIPO (PCT)
Prior art keywords
melt
extruded material
image forming
roller
forming apparatus
Prior art date
Application number
PCT/JP1999/002193
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English (en)
Japanese (ja)
Inventor
Tatsuya Higuchi
Masami Kato
Original Assignee
Daikin Industries, Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Daikin Industries, Ltd. filed Critical Daikin Industries, Ltd.
Publication of WO1999059034A1 publication Critical patent/WO1999059034A1/fr

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Classifications

    • 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
    • G03G15/20—Apparatus for electrographic processes using a charge pattern for fixing, e.g. by using heat
    • G03G15/2003—Apparatus for electrographic processes using a charge pattern for fixing, e.g. by using heat using heat
    • G03G15/2014—Apparatus for electrographic processes using a charge pattern for fixing, e.g. by using heat using heat using contact heat
    • G03G15/2053—Structural details of heat elements, e.g. structure of roller or belt, eddy current, induction heating
    • G03G15/2057—Structural details of heat elements, e.g. structure of roller or belt, eddy current, induction heating relating to the chemical composition of the heat element and layers thereof
    • 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
    • C08K3/16—Halogen-containing compounds

Definitions

  • the present invention is based on a melt extruded material suitable for forming an outermost layer of a fixing roller in a fixing portion of an image forming apparatus, and a fixed material formed using the material. Regarding the fixed mounting roller of the wearing part. Background technology
  • Fluororesin has excellent surface lubricity, mechanical properties, mechanical properties, and abrasion resistance in addition to chemical and thermal stability, and it has excellent transfer properties for electronic materials. It is widely used in body and image forming parts.
  • a conductive material into a fluororesin composition.
  • the conductive material include carbon black, graphite powder, carbon material such as carbon fiber, and metal powder.
  • the conductivity required by the application is different, and in the application as described above, the volume resistivity is 10%. If the composition is less than 8 ⁇ ⁇ cm, the lower the composition, the better. The composition in a range not sacrificing other characteristics of the fluororesin composition. To be elected .
  • the fixed roller of an electronic duplicator has an electrostatic offset (the roller is charged by friction with a paper sheet, and the unfixed toner is not fixed).
  • the fixed image is disturbed, as described above.
  • product-specific resistance rate 1 0 8 ⁇ ⁇ cm or less under the Oh Re if low BUT MUST low have nearly as have the good or.
  • the hot offset the toner heated and melted by the roller attached to the roller attached to the roller and the fixed image was disturbed. In order to prevent such a phenomenon, it is required to have an excellent non-stick property.
  • an image forming apparatus for an OHP sheet is formed by an image forming apparatus such as a copying apparatus.
  • the present invention relates to a melt-extrusion material suitable for forming the outermost layer of a fixing roller in a fixing portion of an image forming apparatus, and in particular, a control of a volume-specific resistivity.
  • Melting extruded material made of fluororesin which is easy to use, has excellent non-adhesiveness, and is excellent in smoothness and strength, and a fixing roller using the same.
  • the purpose is to provide Disclosure of the invention
  • the present invention relates to a composition
  • a composition comprising (A) at least a partially fluorinated filler and (B) a fluorine-containing thermoplastic resin. and Oh Tsu any objects, the e la Re that volume-specific resistivity of the front surface of the film 1 0 8 ⁇ 1 0 1 4 Omega cm, vs. water contact angle 1 0 0 degree or more on your good beauty coat 1 Stretching force at 50 ° C Establishing an image-forming device characterized by being composed of a composition that is not less than 350% The melt extrusion material suitable for forming the outermost layer of the fixed roller in the part, and the development of the fixed roller formed by using the material. The best form for carrying out the lighting
  • the molten extruded material of the present invention has at least a partially fluorinated filler (A) and a fluorine-containing material. It is made of thermoplastic resin ( ⁇ ).
  • At least a part of the filler, at least part of which is a fluorinated material may be a carbon black, a carbon fiber, a petroleum coke, It is preferable to use a carbon material such as graphite powder that has been fluorinated.
  • the fluoridation power obtained by fluorinating a carbon black is particularly important for carbon black, especially for carbon atoms.
  • Fluorinated carbon blacks whose nitrogen atom ratio FZC is 0.1 or more and less than 1.0, particularly 0.1 or more and less than 0.5 are preferred. Sile .
  • FC of the fluorinated carbon black of the component (A) is less than 0.1, the effect of fluorination is insufficient, and the charcoal before fluorination is carbonized.
  • the problem with the raw materials is that the rate of change of the resistance with respect to the compounding amount is extremely large, and it is difficult to control the conductivity.
  • the dispersion of the fluorinated carbon black may be uneven due to the generated structure, or the obtained composition may be hardened. The problem that it became worse remains.
  • FZC is 1.0 or more, it is impossible to impart the intended conductivity to the composition.
  • FZC is measured as follows. Only come only wrapped in filter paper the full Tsu element ⁇ spoon force one Bonn blanking rack to be and the co-retardant N a 2 ⁇ 2 your good beauty Po Li et Chi-les-down off I-le-time, the oxygen
  • the hydrogen fluoride generated by burning in the sealed hermetically sealed flask is used as a fluoride ionometer (Orion Corporation: Ion Anara) Measurement using a conventional method. This value is used to calculate the fluorine content. Calculate FZC based on the obtained fluorine content.
  • the fluorinated carbon black (A) is composed of poly (carbon monofluoride) as the main component, and the average Particle size from 0.01 to 50 m, preferably from 0.01 to: Carbon black of L / zm is fluorinated with fluorine gas.
  • the power is good. Fluorination obtained from carbon material with an average particle size of more than 50 zm, such as petroleum coke, graphite powder, carbon fiber, etc. Forced black black must be used in large amounts to impart conductivity and non-stickiness to the resin, and the resulting composition must have a high surface roughness. There is a tendency for inconveniences such as an increase in surface roughness, a decrease in mechanical strength, and an uneven resistivity.
  • the carbon black suitable for the carbon black (A) is the carbon black having the above-mentioned average particle size.
  • the carbon black is, for example, a rubber black rubber (for example, Asahi # 55 manufactured by Asahi Carbon Co., Ltd.). ), Color breaker channel (for example, Colevia Carbon, Inc., Leven 700.), thermal breaker Commercially available products such as (Sevacarbo MT-C1 manufactured by Colombia Power-Ibon Co., Ltd.) can be used.
  • Conductive power one Bonn Bed rack has an average particle size have small (average particle size below 0. 1 m), the table area has come a large (N 9 surface area 5 0 m 2 Z g or more on ) Structural development (oil absorption lOOcc Zg or more), few impurities (ash content less than 0.1%), graphite It is defined by the factor that the progress of the process progresses, and it is possible to impart conductivity to the material with a relatively small amount of compounding. It is widely used.
  • ketch black EC ketch black EC — 600 JD (hereinafter, ketch black). Ink Yuichi National Co., Ltd.), Black Pearls 200, Vulcan XC—72, CSX—99 (hereafter referred to as Black Black) Co., Ltd.), Denka Black (Electrochemical Engineering Co., Ltd.), Conductex 950 (Colombia Carbon Co., Ltd.), etc. Is on the market.
  • the fluorine carbon black (A) used in the present invention is such that the carbon material can be used in a temperature range of 200 to 600 ° C. It is obtained by contacting fluorine gas at a temperature of more preferably at a temperature in the range of 300 to 500 ° C. At a reaction temperature lower than this range, the progress of the fluorination reaction is slow, the degree of fluorination is not strong, and the thermal stability is not sufficient. The problem arises that the properties such as non-stickiness and lubricity inherent to the fluorinated carbon black are not exhibited. Conversely, at reaction temperatures higher than this range, pyrolysis reactions are more likely to occur, and the yield of the resulting fluorinated carbon black is lower. It gets worse. In addition, it is necessary to pay close attention to the fact that a sudden thermal decomposition reaction may occur and the explosion may occur.
  • the fluorine gas used in the reaction may be diluted with an inert gas such as nitrogen, argon, helium, or carbon tetrafluoride.
  • an inert gas such as nitrogen, argon, helium, or carbon tetrafluoride.
  • the reaction can be performed at normal pressure, but can be performed under reduced pressure or pressurized pressure. Even so, it's hard to find anything.
  • reaction time depend on the reactivity of the raw material carbon material with fluorine and the desired FZC (fluorine content). It may be adjusted as needed.
  • a feature of the present invention is to provide a fluorine-containing thermoplastic resin material that can be melt-extruded and formed.
  • rubber materials such as fluorine rubber and silicone rubber have been used in this field, but materials mainly made of these rubbers are used. Cannot be melt extruded.
  • Fluoro-containing thermoplastics include tetrafluoroethylene (TFE) and at least one other copolymer that can be co-polymerized with it.
  • TFE tetrafluoroethylene
  • Lenically unsaturated monomers for example, olefins such as ethylene and propylene, hexafluoropropylene, vinylidene, etc.
  • Octa-fluorinated olefins such as fluoride, black mouth, trifluorene, bifluoride, etc.
  • Copolymers with polyalkylene vinyl ethers, etc. polyclonal trifluoroethylene, polyvinylidenefluora The power is increased.
  • Particularly preferred fluoro-thermoplastic resin containing fluorine has a high surface temperature of 150 ° C. or more because the surface temperature of the fixed part roller is high.
  • Thermoplastic resin is improved in terms of heat resistance and non-adhesiveness.
  • TFE tetrafluoroethylene
  • HFP hexafluoropropylene
  • TFE No ° —Fluoro (alkyl vinyl ether) -based copolymer
  • Nil ether 99.7. 0.3 to 85 Z15.
  • thermoplastic resins When these fluorine-containing thermoplastic resins are used, they have superior heat resistance, non-adhesion, water / oil / oil repellency, lubricity, and chemical resistance compared to general-purpose resins. The effect is obtained that a composition having the following is obtained.
  • general-purpose resins include, for example, polyether ether ketone, thermoplastic polyimid, polyethylene naphthalate, and the like. , Polybutylene naphthalate, polyether sulfone, polysalphone, polyforce component, polyaryt, poly Non-fluorothermoplastic resins such as libutylene terephthalate and polyethylenitrile can be used.
  • composition ratio of the component (A) and the component (B) is 1Z99 to 20/80 (weight ratio; the same applies hereinafter). If the amount of the component (A) is too small, the effect of adding the fluorinating power is not sufficient, and if the amount is too large, the tensile strength is reduced. Which mechanical strength tends to decrease. Further, in addition to the component (B), the above-mentioned non-fluoroplastic thermoplastic resin may be mixed within a range where the effect of the present invention is not impaired.
  • the characteristics of the melt-extrusion material of the present invention are as follows: good extrusion formability can be obtained without adding a plasticizer, and no surfactant is added. The point is that stable semiconductivity can be obtained. Therefore, in the past, leaching (bleeding) has been a problem and has been a source of contamination. And the addition of a fluorine-based surface active agent can be eliminated.
  • composition of the present invention can be mixed and prepared by a usual method such as a rapid method.
  • Resin and fluorinated carbon black and, if necessary, minimal additives V-type blender, tumbler, henchel mixer After mixing with a mixing machine such as sa, a twin-screw Mix using a melting and kneading device such as an output machine to form a pellet.
  • the pellets obtained in this way are extruded and formed into the desired shape using an extruder, such as tubes, plates, films, etc. It is formed.
  • the melt-extrusion material of the present invention has suitable physical properties as a molding material of the outermost layer of a fixing roller in a fixing section of an image forming apparatus.
  • the coatings (films, tubes, etc.) obtained by melting and extruding the material of the present invention have the following physical properties.
  • the surface has a fixed volume resistivity value of 10 8 to 10 14 ⁇ ⁇ cm. As long as it is within this range, excellent anti-static offset resistance is achieved. In addition, the ratio of the maximum value of the volume-specific resistance to the minimum value of the specific resistance on the surface of the same film, Z, is 10 or less, and the semiconductivity is uniform. It is difficult.
  • the contact angle with water is at least 100 degrees, preferably at least 102 degrees. When the contact angle with water is large, the non-adhesiveness is good.
  • the elongation (150 ° C) is 350% or more, preferably 360% to 450%.
  • the surface roughness (R a) is preferably 5 m or less, and more preferably 0.5 m or less.
  • a smooth surface having a small surface roughness (R a) has less toner remaining and is excellent in image forming properties.
  • the present invention is used as a pressurized roller for the fixing part that is the target of the present invention, it is required to be able to follow the rubber layer.
  • a fixing material that satisfies the characteristics (1), (2), and (4) and provides a large stretch, that is, provides a followability.
  • the material of the present invention can provide various forms of molded products by the melt extrusion molding method. For example, it can be formed into a molded product such as a film, a tube, or a plate. Such a melt-extruded molded product cannot be homogeneous unless it is excellent in melt formability.
  • melt flow rate which is one of the indicators of melt formability
  • MFR melt flow rate
  • the present invention also relates to a fixing roller of a fixing portion of the image forming apparatus.
  • the image forming apparatus includes an electronic photocopier, a facsimile, a laser printer, and the like.
  • the present invention is not limited to these, and includes devices for transferring toner based on electrostatic duplication.
  • An image forming apparatus for example, a fixing portion of an electronic copying machine usually has a heat roller and a pressure roller which are semiconductive rollers. In the present invention, these are collectively referred to as fixed rollers.
  • the stationary roller is heated and pressurized while the recording paper carrying the toner image is conveyed by a heat roller and a pressure roller while being nipped and conveyed. The image is fixed on the recording paper.
  • Such a heat roller is formed by forming a core metal having a heating mechanism into a cylindrical shape by using a conventional melt-extrusion molding method using the melt-extrusion material of the present invention. It is obtained by covering due to heat shrinkage.
  • the pressurizing port roller has a conductive elastic layer formed first on the conductive support. It is.
  • the material for the conductive elastic layer is not particularly limited, but may be silicone rubber, ethylene propylene rubber, or epoxy rubber.
  • Conductive powders and conductive fibers are contained in synthetic rubbers such as rubber rolls, rubber rolls, and rubber. is formed by Tsu by the mosquito turbo etc. emission fibers), etc.
  • volume resistivity is 1 0 5 ⁇ ⁇ cm or less, good or to rather is 1 0 3 ⁇ ⁇ cm or less
  • a rubber hardness (JISA) force in the range of 20 to 50 degrees, preferably 25 to 40 degrees is used.
  • plasticizers or surfactants for the purpose of resistance adjustment or rubber hardness adjustment. . This means that these agents ooze out over time, contaminating the surface of the photosensitizers and other surfaces, and removing the toner film on the roller surface. It is a cause of the occurrence.
  • the material of the conductive support is not particularly limited, and the alloy or the alloy mainly composed of aluminum or aluminum is used. Tenres can be used.
  • melt-extruded material is formed into a tube by the usual melt-extrusion forming method of the present invention. It may be stretched or heat-shrinkable if necessary, but usually does not have to be stretched or heat-shrinkable.
  • the thickness of such a tube must be in the range of 0.01 to 0.15 mm, and it is preferable to deviate from this value. No rubber mouth is available.
  • the tube obtained in this way is used as a pressurizing rubber roller for constant mounting by coating the surface of a normal fixing rubber roller.
  • a rubber roller can generally be exemplified by a rubber core attached to a rubber core.
  • the rubber is silicone-based elastomer, and fluorine-based elastomer.
  • the core metal and the tube according to the present invention are arranged inside the tubular molded body with a space between them, and there is no tubular molded body. Arrange so that the surface and the outer surface of the tube are in contact with each other. Pour the material for the conductive elastic layer into the space described above, and if necessary, By vulcanizing, the pressurized rubber roller for stationary application of the present invention can be obtained. Of course, it is necessary to take out the roller part including the covered tube from the cylindrical molded body when necessary.
  • a conductive elastic layer may be prepared in advance, and the surface thereof may be coated with the tube of the present invention.
  • a heat-shrinkable tube as the tube S.
  • the melt-extrusion material of the present invention is suitable as a material for a fixing roller in a fixing section of an image forming apparatus, particularly, a material for a pressurized roller. .
  • Parts represent parts by weight.
  • Fluorocarbon carbon black (denka black manufactured by Electrochemical Engineering Co., Ltd., average particle size 0.04 m) is fluorinated to obtain FZC Has created a 0.1-inch fluorine pump.
  • JISK6911 resistance measurement cell (Registration channel R12702A) manufactured by Adon'nst Co., Ltd. And a ohmmeter (Digital ultra-high ohmmeter R834OA).
  • a surface roughness meter (Surfcom 47 OA) manufactured by Tokyo Seimitsu Co., Ltd., a diamond pick-up with a 2 mR stylus tip is used for the measurement.
  • the 2.5 mm pull surface is automatically measured at a pick-up speed of 0.3 mmsec.
  • Ra is the center line average roughness specified in JISB0601-19882.
  • melt flow rate was measured according to ASTMD 3307 (372 ° C, load 5 kg). The results are shown in Table 1.
  • Example 1 PFA alone was not melt-extruded and molded without blending the fluorine-containing carbon black to prepare a file, and each physical property was measured. . Table 1 shows the results.
  • Example 1 the raw material carbon black (non-fluorinated) instead of the fluorine black carbon black (Electrochemical Science) was used. Denka black manufactured by Kogyo Co., Ltd. The average particle size of 0.04 m) was mixed in the amount shown in Table 1 and the melt extrusion was performed in the same manner as in Example 1. Films were produced by molding and each physical property was measured. The results are shown in Table 1.
  • Example 1 In the same manner as in Example 1 except that the amounts shown in FIG. Films were formed by molding and the physical properties were measured. Table 1 shows the results.
  • melt-extrusion material of the present invention is excellent in melt formability (MFR), and the material of the fluorinated carbon black is also excellent. Even if the amount is changed, the change in the volume-specific resistance is small (compare Examples 2 and 3, and 4 and 5), non-adhesive (contact angle with water) and smoothness It provides a molded product that excels in (surface roughness) and has sufficient elongation and is suitable for the fixing roller in the fixing part.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)

Abstract

L'invention concerne un matériau extrudé par fusion se prêtant à l'élaboration d'un rouleau fixateur de dispositif de formation d'image, qui présente une excellente aptitude au moulage par fusion, qui a une résistivité stable au moulage en film de revêtement, qui n'adhère pas, et qui présente aussi d'excellentes qualités de lissé et d'allongement. Le matériau est une composition qui comprend (A) une charge dont au moins une partie est fluorée et (B) une résine thermoplastique à base de fluor, et les caractéristiques dudit matériau sont les suivantes: résistivité comprise entre 10?8 et 1014¿ Φ.cm lorsque le matériau est formé en film de revêtement, angle de contact avec l'eau supérieur à 100°, rugosité de surface inférieure à 0,5 νm, et possibilité d'allongement de plus de 350 % à 150 °C lors du moulage en film de revêtement.
PCT/JP1999/002193 1998-05-13 1999-04-26 Materiau extrude par fusion se pretant a l'elaboration de la couche exterieure d'un rouleau fixateur de dispositif de formation d'image WO1999059034A1 (fr)

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Application Number Priority Date Filing Date Title
JP13081098 1998-05-13
JP10/130810 1998-05-13

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WO1999059034A1 true WO1999059034A1 (fr) 1999-11-18

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004040380A1 (fr) * 2002-10-31 2004-05-13 Hot Tech Ab Fabrication d'un rouleau de thermofixage
US8285184B2 (en) * 2009-01-21 2012-10-09 Xerox Corporation Nanocomposites with fluoropolymers and fluorinated carbon nanotubes
US8787808B2 (en) 2007-06-22 2014-07-22 Konica Minolta, Inc. Fixing device including fixing members for applying pressure on a conveyed sheet

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01201687A (ja) * 1988-02-06 1989-08-14 Arai Pump Mfg Co Ltd 定着ローラー
JPH06279603A (ja) * 1993-03-25 1994-10-04 Daikin Ind Ltd フッ素樹脂成形体およびその製法
JPH07149448A (ja) * 1993-10-05 1995-06-13 Daikin Ind Ltd 導電性および非粘着性を付与しうる組成物、該組成物を用いた塗料ならびにローラ
JPH08150671A (ja) * 1994-11-28 1996-06-11 Ricoh Co Ltd 離型性ローラ及びその製造方法
JPH0954506A (ja) * 1995-06-06 1997-02-25 Canon Inc 画像形成装置及び中間転写体
JPH09169917A (ja) * 1995-12-18 1997-06-30 Ricoh Co Ltd 帯電防止性樹脂組成物
JPH09185282A (ja) * 1995-12-28 1997-07-15 Nitto Kogyo Co Ltd 電子写真定着用オイル塗布ロール及びその製造法
JPH09324128A (ja) * 1996-06-05 1997-12-16 Daikin Ind Ltd フッ化カーボン組成物、塗料および画像形成部材ならびに複合材料および製法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01201687A (ja) * 1988-02-06 1989-08-14 Arai Pump Mfg Co Ltd 定着ローラー
JPH06279603A (ja) * 1993-03-25 1994-10-04 Daikin Ind Ltd フッ素樹脂成形体およびその製法
JPH07149448A (ja) * 1993-10-05 1995-06-13 Daikin Ind Ltd 導電性および非粘着性を付与しうる組成物、該組成物を用いた塗料ならびにローラ
JPH08150671A (ja) * 1994-11-28 1996-06-11 Ricoh Co Ltd 離型性ローラ及びその製造方法
JPH0954506A (ja) * 1995-06-06 1997-02-25 Canon Inc 画像形成装置及び中間転写体
JPH09169917A (ja) * 1995-12-18 1997-06-30 Ricoh Co Ltd 帯電防止性樹脂組成物
JPH09185282A (ja) * 1995-12-28 1997-07-15 Nitto Kogyo Co Ltd 電子写真定着用オイル塗布ロール及びその製造法
JPH09324128A (ja) * 1996-06-05 1997-12-16 Daikin Ind Ltd フッ化カーボン組成物、塗料および画像形成部材ならびに複合材料および製法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004040380A1 (fr) * 2002-10-31 2004-05-13 Hot Tech Ab Fabrication d'un rouleau de thermofixage
US8787808B2 (en) 2007-06-22 2014-07-22 Konica Minolta, Inc. Fixing device including fixing members for applying pressure on a conveyed sheet
US8285184B2 (en) * 2009-01-21 2012-10-09 Xerox Corporation Nanocomposites with fluoropolymers and fluorinated carbon nanotubes

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