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WO2007091695A1 - Corps protecteur en résine thermoplastique - Google Patents

Corps protecteur en résine thermoplastique Download PDF

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Publication number
WO2007091695A1
WO2007091695A1 PCT/JP2007/052428 JP2007052428W WO2007091695A1 WO 2007091695 A1 WO2007091695 A1 WO 2007091695A1 JP 2007052428 W JP2007052428 W JP 2007052428W WO 2007091695 A1 WO2007091695 A1 WO 2007091695A1
Authority
WO
WIPO (PCT)
Prior art keywords
layer
fluororesin
covering
filler
cohesive failure
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/JP2007/052428
Other languages
English (en)
Japanese (ja)
Inventor
Keigo Goshiki
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Junkosha Co Ltd
Original Assignee
Junkosha Co 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 Junkosha Co Ltd filed Critical Junkosha Co Ltd
Publication of WO2007091695A1 publication Critical patent/WO2007091695A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/704—Crystalline

Definitions

  • the present invention relates to a non-adhesive material used in the manufacture of a roll having a non-adhesive surface made of a fluororesin on the surface, such as a fixing roll for fixing toner onto paper or the like in a copying apparatus, a printer, or the like. It relates to a covering. Background art
  • Fluororesin has properties such as heat resistance, chemical resistance, and non-adhesiveness, and these properties are used in various applications.
  • image forming apparatuses such as copiers and printers using non-adhesiveness and heat resistance
  • it is used as a fixing roll of a fixing device that heats and fixes a toner image transferred to paper or the like.
  • the fixing roll is attached to the surface of the substrate with a heat-shrinkable fluororesin coating and heated to be integrated with the lower layer.
  • a method of injecting and integrating an adhesive synthetic resin composition between a substrate attached to the surface of a substrate and the substrate is also known as a fluororesin coating layer.
  • the fluororesin is non-tacky, it can be used not only for directly coating a metal substrate, but also when the adhesive composition is injected to bond the substrate and the coated body. There was a problem that the adhesion of the layers was insufficient.
  • the inner surface of the coated body is etched to improve the adhesion characteristics, or a two-layer structure in which a filler-filled layer is formed on the inner surface of the coated body. It has been proposed to improve the adhesion by etching the surface of the inner layer.
  • the etched fluorine resin has a problem that the activity of the etching surface is deteriorated with time due to heat, ultraviolet rays, etc., and as a result, the adhesion to the substrate is lowered. For this reason, when used in places where the temperature is high, such as a heat fixing roll, the adhesive strength with the substrate decreases with the lapse of time, and the adhesive peels off from the mouthpiece main body, resulting in a problem in adhesive stability.
  • the present invention provides a fluororesin coating for covering the surface of a fixing roll or the like, and etching the coating with a large surface non-tackiness, good adhesion of the inner surface layer, and excellent adhesion stability over time. The issue is to provide without passing.
  • An object of the present invention is to provide a coated body made of a thermoplastic resin, comprising an outer layer made of a thermoplastic fluorine resin and an inner surface layer of a thermoplastic fluororesin having a hydroxyl group containing a filler having a flaky crystal structure.
  • the surface of the layer is not etched and can be solved by a coating.
  • the thermoplastic fluororesin is a perfluoroalkoxyalkylene polymer. It is a covering made of the above thermoplastic resin.
  • the filler having the flaky crystal structure is a covering made of the above thermoplastic resin, wherein the filler is at least one selected from hexagonal boron nitride, graphite, talc, activated clay, acid clay, kaolin clay, and bentonite.
  • the coated body having a non-adhesive surface of the present invention comprises a non-adhesive outer layer made of a thermoplastic fluororesin and an inner surface layer made of a thermoplastic fluororesin having a hydroxyl group containing a filler having a flaky crystal structure.
  • the surface of the inner surface layer has an adhesive surface without being subjected to etching treatment, the adhesion with the substrate is good, the change in the adhesive property with time is small, and the surface is non-tacky. A good covering can be provided.
  • FIG. 1 is a view for explaining infrared absorption spectra of fluororesins used in Examples and Comparative Examples of the present invention. BEST MODE FOR CARRYING OUT THE INVENTION
  • an inner surface layer of a covering having a non-adhesive fluororesin surface layer a layer in which a filler having a flaky crystal structure as a filler is blended in a fluororesin having a hydroxyl group is formed. It has been found that it is possible to improve the adhesion of the fluororesin without etching the inner surface layer.
  • the coated body made of the fluorocoagulant of the present invention has good adhesion without etching the surface of the inner surface layer.
  • the reason why it is possible to form an adhesive layer that does not change over time is not clear, and such a situation was completely unexpected.
  • the fluororesin constituting the non-adhesive outer layer of the coated body of the present invention include perfluoroolefin-alkoxyalkane polymer (PFA), perfluoroethylene propylene copolymer (FEP), and ethylene-tetrafluoroethylene copolymer.
  • thermoplastic fluororesins such as (ETFE), polychlorotrifnoreo ethylene (PC TFE), ethylene-chlorotrifnoreo ethylene copolymer (ECT FE), and polyvinylidene fluoride (PVdF).
  • EFE polychlorotrifnoreo ethylene
  • ECT FE ethylene-chlorotrifnoreo ethylene copolymer
  • PVdF polyvinylidene fluoride
  • perfluoroalkoxyalkane polymer PFA has good heat resistance and non-adhesive properties.
  • additives such as antistatic agents may be added to the non-adhesive outer layer of the covering.
  • antistatic agent include conductive fillers such as carbon black and carbon nanotubes.
  • the fluororesin constituting the inner layer of the coated body of the present invention is the same as the thermoplastic fluororesin used as the material for the non-adhesive outer layer, and has the same basic chemical structure as a heat having a hydroxyl group.
  • a plastic fluororesin can be used.
  • the covering of the present invention is composed of two layers, an outer layer and an inner layer, the fluororesin constituting the outer layer and the inner layer has the same basic chemical structure, and a material having a hydroxyl group introduced into the inner layer. Is preferably used.
  • thermoplastic fluororesin having a hydroxyl group can be produced by copolymerization using a fluorinated ethylenic monomer having a hydroxyl group and an ethylenic monomer having no hydroxyl group.
  • X and X 1 are the same or different, both are hydrogen atoms or fluorine atoms
  • R f is a divalent alkylene group having 1 to 40 carbon atoms, a fluorinated oxyalkylene group having 1 to 40 carbon atoms, carbon number Fluorine-containing alkylene group containing 1 to 40 ether bonds or 1 to 40 carbon atoms Represents a fluorine-containing oxyalkylene group containing an ether bond.
  • fluorine-containing ethylenic monomer having a hydroxyl group more specifically,
  • CF 2 CF— R — CH 2 OH
  • Rf 1 is a divalent fluorine-containing alkylene group having 1 to 40 carbon atoms or one OR, where R / is a divalent fluorine-containing alkylene group having 1 to 40 carbon atoms or 1 to 40 carbon atoms. It is a divalent fluorine-containing alkylene group containing an ether bond.
  • CF 2 CFCF 2 — OR f 3 — CH 2 OH
  • R f 3 represents a divalent fluorine-containing alkylene group having 1 to 39 carbon atoms or a divalent fluorine-containing alkylene group containing an ether bond having 1 to 39 carbon atoms.
  • one R f 4 is a divalent fluorine-containing alkylene group having 1 to 39 carbon atoms, or one OR / (R is a divalent fluorine-containing alkylene group having 1 to 39 carbon atoms or an ether having 1 to 39 carbon atoms. A divalent fluorine-containing alkylene group containing a bond).
  • Rf 6 is a divalent fluorine-containing alkylene group having 1 to 40 carbon atoms.
  • the coated body according to the present invention is characterized in that a filler having a flaky crystal structure is blended as a filler in a fluorine resin layer of an inner surface layer, and as a result of blending a boiler having a flaky crystal structure,
  • the adhesive properties of the layer were improved without any surface treatment such as etching.
  • Examples of the substance having a flaky crystal structure that can be used for the inner surface layer include clay minerals such as hexagonal boron nitride, graphite, talc, activated clay, acid clay, kaolin clay, and bentonite.
  • the content of the filler having a flaky crystal structure is preferably from 0.01 to 40 parts by weight per 100 parts by weight of the fluororesin.
  • the filler can be blended into the fluororesin by melting the fluororesin and mixing the filler, mixing a certain amount of filler into the thermoplastic fluororesin pellets and powder, and biaxial or uniaxial. A method of mixing using an extruder or a method of preparing a high-concentration filler master patch in advance and mixing at the time of molding can be used.
  • the coated body of the present invention can produce a multilayer tube by various methods, but is preferably produced by an annular multilayer extrusion method.
  • a covering made of seamless tubes can be produced by attaching an annular die to a plurality of extruders and forming a film by coextrusion.
  • the formed multilayer tube-like film can be imparted with a predetermined characteristic to the heat shrinkage rate and the like by performing stretching, heat treatment and the like.
  • the covering of the present invention may have a predetermined number of intermediate layers in addition to the case where the outer layer and the inner layer are composed of two layers, and by providing a layer having predetermined characteristics as the intermediate layer. The characteristics of the covering can be adjusted as appropriate. Next, a method for mounting the covering of the present invention on the surface of the mouthpiece and integrating it with the mouthpiece will be described.
  • the first method is to form an elastic layer of a predetermined thickness made of silicone rubber, urethane rubber, fluororubber, or a foam of these rubbers on the outer peripheral surface of a metal core made of a metal cylinder or column. Then, an adhesive layer is provided on the surface, and then the coated body of the present invention is coated.
  • the second method is a method of coating the coated body of the present invention after providing an adhesive layer having a predetermined thickness on the outer peripheral surface of the metal core.
  • the third method is to dispose the cover of the present invention at a predetermined distance from the outer peripheral surface of the metal core, and unvulcanized silicone rubber between the outer peripheral surface of the metal core and the cover. And then vulcanizing and integrating the metal core, the silicone rubber, and the covering.
  • the adhesive strength of the cover even in the method of rolling and shifting, it is preferable to bond at a temperature not lower than the melting point and not higher than the melting point of the thermoplastic fluororesin having a hydroxyl group in the inner layer of the cover.
  • the adhesion time can be shortened and the adhesive strength can be increased.
  • the adhesive is bonded at a temperature higher than the melting point, the covering is deformed, causing problems such as unevenness on the surface.
  • the covering can be heated to a predetermined temperature in the step of integrating the covering. Further, in the third method, heat treatment can be performed by heating to a predetermined temperature after the covering is bonded and integrated.
  • a primer is applied to the inner surface of the cover.
  • the present invention will be described below with reference to examples.
  • Perfluoroalkoxyalkane polymer (Teflon 451 HP J from Mitsui Dupont Chemicals) is used as the outer layer material, and 1% by mass of hexagonal boron nitride (HP-PI from Mizushima alloy iron) is used as the inner layer material.
  • a thermoplastic fluororesin (Neoflon PFA RAP manufactured by Daikin Industries) was used.
  • the outer layer hopper and inner layer hopper of the two-layer extruder are filled with the outer layer material and the inner layer material, respectively, and each is introduced into a two-layer annular die, the outer diameter is 35 mm, the outer layer thickness is 45 ⁇ , the inner surface A covering of Sample 1 having a two-layer structure with a layer thickness of 5 m was formed.
  • An aluminum metal core was placed in the center of the cylindrical mold, and the inner surface of the sample was primed with an additive-type silicone rubber primer (GE Toshiba Silicone XP 8 1 -A6361 (A) (B)) After coating two types of coatings and non-primer coatings concentrically on the metal core, adding unvulcanized mixture of catalyst and scavenger between the metal core and the coating Press-fit type silicone rubber, 130. The primary vulcanization was performed for 30 minutes at C and the secondary vulcanization was performed at 150 ° C for 4 hours.
  • an additive-type silicone rubber primer GE Toshiba Silicone XP 8 1 -A6361 (A) (B)
  • the roll immediately after production and the roll after the heating test that was left in a constant temperature bath at 230 ° C for 1500 hours were cut into a width of 10 mm and a length of 10 Omm, respectively, and a part of the covering was peeled off from the end of the tool body. End of tensile tester The peel strength was measured at a speed of 5 OminZ, and the results are shown in Table 2.
  • Samples of 100 / im in thickness were prepared for each of the Daikin Kogyo PFA RAP made by Daikin Industries and the Teflon 451 HP J made by Mitsui DuPont Fluorochemicals, which are fluororesins used in Examples and Comparative Examples.
  • the absorption spectrum was measured with an external spectrometer (FT / IR-4100 manufactured by JASCO). The results are shown in Fig. 1 as sample 1 (neoflon PFA RAP) and sample 2 (Teflon 45 1 HPJ).
  • Sample 1 and Sample 2 are both made of PFA, but Sample 1 has an absorption showing hydroxyl groups at 3640 cm- 1 , but Sample 2 has no such absorption showing hydroxyl groups. There wasn't.
  • Samples 2-7 were prepared in the same manner as Sample 1 except that the filters listed in Table 1 as Samples 2-7 in Table 1 were used as inner layer forming filters, and each sample was primed. Samples 2-7 were prepared in the same manner as in Example 1 and those not primed were prepared, and evaluated by the evaluation method described in Example 1. The results are shown in Table 2. It was described in.
  • Teflon 451 HP J made by Mitsui DuPont Fluoro Chemical Co., Ltd. was introduced into the hopper of the extruder as a perfluoroalkoxy alcohol polymer, and was introduced into the annular die from the extruder. A one-layered coating was obtained.
  • Perfluoroalkoxyalkane polymer (Teflon 451 HP J made by Mitsui Dupont Chemical) was used as the outer layer material, and thermoplastic fluororesin (Nephron PF A RAP made by Daikin Industries) was used as the inner layer material. Except as in Example 1, a coated body of Comparative 2 was prepared, coated on a metal roll in the same manner as in Example 1, and the peel strength was measured in the same manner as in Example 1. The results are shown in Table 2. Described.
  • the coated body having a non-adhesive surface of the present invention comprises a non-adhesive outer layer comprising a resin layer made of a thermoplastic fluororesin, and a hydroxyl group-containing thermoplastic fluororesin layer containing a filler having a flaky crystal structure. Since the inner surface has an adhesive layer with good adhesion and the outer surface has a non-adhesive layer, it has good adhesion to the substrate and little change in the adhesive properties over time. A coated body having good surface non-tackiness can be provided.

Landscapes

  • Laminated Bodies (AREA)
  • Fixing For Electrophotography (AREA)

Abstract

L'invention concerne un corps protecteur en résine thermoplastique qui comprend une couche extérieure composée d'une fluororésine thermoplastique et une couche intérieure composée d'une fluororésine thermoplastique comprenant un groupe hydroxyle et contenant une charge présentant une structure cristalline laminaire. La surface de la couche intérieure n'est pas soumise à une gravure. Ce corps protecteur comprend une couche superficielle non adhésive et une couche intérieure qui présente une bonne adhérence à une base ou analogue.
PCT/JP2007/052428 2006-02-07 2007-02-05 Corps protecteur en résine thermoplastique Ceased WO2007091695A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2006030204A JP2007210134A (ja) 2006-02-07 2006-02-07 熱可塑性樹脂からなる被覆体
JP2006-030204 2006-11-06

Publications (1)

Publication Number Publication Date
WO2007091695A1 true WO2007091695A1 (fr) 2007-08-16

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2007/052428 Ceased WO2007091695A1 (fr) 2006-02-07 2007-02-05 Corps protecteur en résine thermoplastique

Country Status (3)

Country Link
JP (1) JP2007210134A (fr)
TW (1) TW200738457A (fr)
WO (1) WO2007091695A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6488801B2 (ja) * 2015-03-20 2019-03-27 富士ゼロックス株式会社 管状体、定着装置および画像形成装置

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001315274A (ja) * 2000-05-11 2001-11-13 Du Pont Mitsui Fluorochem Co Ltd フッ素樹脂被覆積層体

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01155377A (ja) * 1987-12-11 1989-06-19 Canon Inc 弾性回転体及び定着装置
JP3105972B2 (ja) * 1991-10-12 2000-11-06 グンゼ株式会社 導電性多層チューブ
JP2002316335A (ja) * 2001-04-23 2002-10-29 Bridgestone Corp ゴムロールの製造方法
JP4033326B2 (ja) * 2001-11-13 2008-01-16 キヤノン化成株式会社 帯電ローラ用被覆チューブの押出し成形金型及びそれを用いた帯電ローラ用被覆チューブの製造方法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001315274A (ja) * 2000-05-11 2001-11-13 Du Pont Mitsui Fluorochem Co Ltd フッ素樹脂被覆積層体

Also Published As

Publication number Publication date
TW200738457A (en) 2007-10-16
JP2007210134A (ja) 2007-08-23

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