WO2004018201A1 - Lamine de fluororesine et procede de production - Google Patents

Lamine de fluororesine et procede de production Download PDF

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Publication number
WO2004018201A1
WO2004018201A1 PCT/JP2003/010113 JP0310113W WO2004018201A1 WO 2004018201 A1 WO2004018201 A1 WO 2004018201A1 JP 0310113 W JP0310113 W JP 0310113W WO 2004018201 A1 WO2004018201 A1 WO 2004018201A1
Authority
WO
WIPO (PCT)
Prior art keywords
fluorine
primer layer
resin
fluorinated
functional group
Prior art date
Application number
PCT/JP2003/010113
Other languages
English (en)
Japanese (ja)
Inventor
Yasutoshi Nakatani
Koichiro Ogita
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.
Priority to JP2004530547A priority Critical patent/JPWO2004018201A1/ja
Publication of WO2004018201A1 publication Critical patent/WO2004018201A1/fr

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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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal 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
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/04—Layered products comprising a layer of natural or synthetic rubber comprising rubber as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B25/08—Layered products comprising a layer of natural or synthetic rubber comprising rubber 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
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/02—2 layers
    • 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
    • B32B2307/30—Properties of the layers or laminate having particular thermal properties
    • B32B2307/306—Resistant to heat
    • 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
    • B32B2311/00—Metals, their alloys or their compounds
    • 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
    • B32B2319/00—Synthetic rubber

Definitions

  • Fluorine-containing laminate and method for producing fluorinated laminate are Fluorine-containing laminate and method for producing fluorinated laminate
  • the present invention relates to a fluorinated laminate, a method for producing the fluorinated laminate, and an office automation device having the fluorinated laminate.
  • Image forming apparatuses such as printing machines and copiers in the field of office automation equipment (OA equipment) have a fixing device for forming an image by fixing toner to a transfer material such as paper.
  • the fixing device usually includes a fixing member such as a roll, a belt, or a film for holding the transfer material.
  • the fixing member is formed from a base material that forms a fixing member such as a drum, a belt, or a film. It becomes.
  • the fixing member has heat resistance and a surface having excellent wear resistance and non-adhesiveness. Therefore, tetrafluoroethylene Z perfluoro (alkyl butyl ether) is required.
  • a laminate is used in which a layer made of a fluorinated resin having excellent heat resistance, abrasion resistance and non-adhesiveness such as a copolymer is laminated on a base material.
  • a method of producing a laminate by laminating a layer made of a fluororesin on a substrate includes (1) using a coating composition containing the fluororesin or a dispersion of the fluororesin as the substrate.
  • a coating method There are known a coating method, and (2) a method in which a resin molded from a fluororesin is applied to a substrate and bonded by heating.
  • Japanese Patent Application Laid-Open No. 2002-1772731 discloses a method in which a primer layer is formed on a base material, and a dispersion composition of a fluororesin powder is coated on the primer layer. A method of mounting is disclosed.
  • the melt viscosity of the fluororesin is low and the molecular weight is low. Since it is a method using a material, there was a problem in terms of durability and abrasion resistance.
  • Method (2) uses an extruder or the like regardless of the molecular weight of the fluororesin. This is a method that can obtain a laminated body that is more excellent in durability and abrasion resistance than the method (1) because a smooth surface can be formed.
  • JP-A-4-153027 discloses a method comprising a tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer having one CF 3 group at a terminal.
  • a method of laminating a tube on a base material it is described that the inner surface of the tube is subjected to an etching treatment such as sodium etching to improve the adhesion between the base material and the tube made of a fluororesin.
  • the etching treatment may use a corrosive etching agent, which may cause operational problems such as handling.
  • Japanese Patent Application Laid-Open No. 9-244444 discloses a tetrafluoroethylene Z-perfluoro (methyl vinyl ether) copolymer in which a metal core is laminated on a substrate coated with a rubber such as a silicone elastomer.
  • a metal core is laminated on a substrate coated with a rubber such as a silicone elastomer.
  • a rubber such as a silicone elastomer.
  • an etching treatment may be performed to improve the adhesion between the base material and the tube, but a primer treatment may be performed on the inner surface of the tube.
  • the primer treatment involves applying a primer to the inner surface of the tube, and requires a skill in the treatment operation, and has a problem that the process is complicated.
  • Japanese Patent Application Laid-Open No. 2002-31997 discloses a tube made of a fluororesin having a specific heat shrinkability, and a tube and a substrate made of a fluororesin without performing an etching treatment. Is described as having good adhesiveness. This publication describes that in Examples, a substrate treated with a primer for a fluororesin paint is covered with a tube made of a fluororesin.
  • An object of the present invention is to provide a fluorine-containing laminate having good adhesiveness without performing an etching treatment in view of the above-mentioned situation, and a method for producing the fluorine-containing laminate.
  • the present invention provides a fluorine-containing laminate comprising a base material, a primer layer formed on the base material, and a molded body layer formed on one of the primers, wherein the base material is the above-mentioned bramer layer
  • the surface on which is formed is made of a heat-resistant rubber, a heat-resistant resin or a metal
  • the primer layer is made of a functional group-containing fluorine-containing ethylenic polymer
  • the molded layer is made of a fluorine-containing resin.
  • a fluorinated laminate characterized by being formed from a fluorinated resin molded article.
  • the present invention relates to a method for producing a fluorine-containing laminate for producing the above-mentioned fluorine-containing laminate, wherein a step of forming a primer layer on a substrate and a step of applying a fluorine-containing resin molded article on the primer layer And a step of heating and bonding the primer layer and the fluorine-containing resin molded article to each other.
  • FIG. 1 is a schematic cross-sectional view of a roll for OA equipment. Explanation of reference numerals
  • the fluorinated laminate of the present invention comprises a substrate, a primer layer formed on the substrate, and a molded layer formed on the primer layer.
  • the substrate on which the primer layer is formed is made of a heat-resistant rubber, a heat-resistant resin or a metal.
  • the “surface forming the primer layer” is a concept that may be a part or all of the surface of the base material as long as it is a site where the primer layer is formed.
  • the whole base material is made of heat-resistant rubber, heat-resistant resin or metal.
  • a part of the base material is made of heat-resistant rubber, heat-resistant resin or metal, and the other part is made of other material other than heat-resistant rubber, heat-resistant resin or metal.
  • the base material for example, the surface on which the primer layer is formed is made of a heat-resistant rubber, a heat-resistant resin, or a metal, and the surface on which the primer layer is not formed is made of a heat-resistant rubber, a heat-resistant resin, or any other material that is not a metal. And two or more layers are formed.
  • the heat-resistant rubber is not particularly limited, and includes, for example, silicone rubber, fluorine rubber and the like, and may be a multilayer product obtained by laminating two or more of these.
  • the heat-resistant rubber is preferably a silicone rubber.
  • the heat-resistant resin is not particularly limited, and examples thereof include a polyimide resin, a polyetherimide resin, a polyamide resin, a polyamideimide resin, a polyethersulfone resin, a polyetherketone resin, a polyetheretherketone resin, and a polyethylene terephthalate.
  • the heat-resistant resin used for the base material is conceptually distinguished from the heat-resistant resin used for the primer layer described below in that it is included in the base material, but is the same as the heat-resistant resin used for the primer layer. They may be of different types or of different types.
  • the metal is not particularly limited, and includes, for example, Eckel, aluminum, stainless steel [SUS], and the like, and may be a multilayer product obtained by laminating two or more of these metals.
  • the metal is preferably nickel, aluminum, or stainless steel.
  • the substrate is preferably a material in which the metal is coated with a heat-resistant rubber, a metal, or a heat-resistant resin.
  • the base material is preferably a core metal, and the core is preferably coated with silicone rubber.
  • Office automation equipment Belt or film for office automation equipment, heat-resistant resin or metal belt or film base, heat-resistant resin or metal belt or film base coated with silicone rubber Preferably, it is
  • the primer layer is made of a functional group-containing fluorine-containing ethylenic polymer.
  • the functional group-containing fluorine-containing ethylenic polymer is a polymer having, as a functional group, a hydroxyl group, a hydroxyl group, a carboxyl group forming a salt, an alkoxycarbonyl group and / or an epoxy group. Means a product obtained by polymerizing an ethylenically unsaturated compound having a fluorine atom directly bonded to a carbon atom.
  • the functional group-containing fluorine-containing ethylenic polymer may have one or more of the above functional groups.
  • the type and combination of the functional groups are appropriately selected depending on the type, purpose, application, and the like of the material for forming the above-mentioned primer layer, but are preferably hydroxyl groups from the viewpoint of heat resistance.
  • the primer layer may be a single layer as long as it is composed of the functional group-containing fluorinated ethylene polymer, or may be a two-layer composed of different types of functional group-containing fluorinated ethylenic polymer. It may be the above.
  • the above-mentioned "carboxyl group forming a salt” means that an atom or an atomic group capable of forming a monovalent or divalent cation is bonded instead of hydrogen of the carboxyl group. Means things.
  • the carboxyl group forming the salt may be one that ionizes in a liquid medium containing water in a dispersion composition described below, for example.
  • the atom or atomic group capable of forming the cation is not particularly limited, and includes, for example, K, Na, Ca, Fe, NH 4 and the like. It may be the same or different in one molecule of the ethylenic polymer and / or between a plurality of molecules.
  • the above-mentioned epoxy group is generally formed by linking two atoms of carbon bonded by a carbon chain to one atom of oxygen, and in the carbon chain between the two atoms of carbon bonded to the oxygen.
  • the number of carbon atoms is not particularly limited.
  • the 1,2-epoxy group and the 1,2-epoxy group are highly reactive and are presumed to easily contribute not only to the chemical bond with the base material but also to the chemical bond with the molded article layer. 1,3-epoxy groups are preferred, and 1,2-epoxy groups are more preferred.
  • the functional group-containing fluorinated ethylenic polymer includes the functional group-containing fluorinated ethylenic monomer (a) having the functional group and the functional group-free fluorinated ethylenic monomer having no functional group. It is obtained by polymerizing (b), and for example, those disclosed in International Publication No. 98/50229 pamphlet and the like can be used.
  • Rf 1 represents a fluorinated alkylene group having 1 to 40 carbon atoms or a fluorinated alkylene group having an ether bond having 1 to 40 carbon atoms.
  • CF 2 CFOCF 2 CF 2 CH 2 OH
  • CF 2 CFO (CF 2 ) 3 COOH
  • CF 2 CFCF 2 CH 2 OH
  • CF 2 CFCF 2 OCF 2 CF 2 CF 2 COOH
  • CF 2 CFCF 2 OCF 2 CFCOOCH 3
  • Each compound represented by is more preferable.
  • Examples of the functional group-free fluorine-containing ethylenic monomer (b) include, for example, tetrafluoroethylene and the following general formula (2)
  • Rf 2 represents an CF 3 or one OR f 3
  • R f 3 represents.
  • Par Furuoroarukiru group of from 1 to 5 carbon compounds represented by the following general formula (3)
  • X 4 represents a hydrogen atom, a fluorine atom or a chlorine atom, and n 2 represents an integer of 1 to 5.
  • the functional group-containing fluorinated ethylenic polymer (a) and the functional group-containing fluorinated ethylenic monomer (a) are used within a range that does not decrease the heat resistance of the obtained functional group-containing fluorinated ethylenic polymer. It may be obtained by copolymerizing an ethylenic monomer having no fluorine atom with the fluorine-containing ethylenic monomer containing no functional group (b). The ethylenic monomer having no fluorine atom has no functional group.
  • the ethylenic monomer having no fluorine atom is preferably an ethylene monomer having 5 or less carbon atoms so as not to lower the heat resistance of the resulting functional group-containing fluoroethylene polymer. Examples thereof include ethylene, propylene, 1-butene, 2-butene and the like.
  • the “ethylenic monomer having no fluorine atom” is characterized in that the functional group-containing fluorine-containing ethylenic monomer (a) and the functional group do not have a functional group or a fluorine atom. This is a different concept from non-containing fluorine-containing ethylenic monomer (b).
  • the content of the functional group-containing fluorinated ethylenic monomer (a) is 0.05 to 30 of the total of the monomers derived from the monomer units in the molecule of the functional group-containing fluorinated ethylenic polymer. Preferably it is mol%.
  • the “monomer unit” means a part of the molecular structure of the functional group-containing fluorine-containing ethylenic polymer, which is derived from the monomer.
  • the polymerization method for obtaining the above functional group-containing fluorine-containing ethylenic polymer is not particularly limited, and a conventionally known polymerization method such as suspension polymerization, polymerization and the like can be used.
  • the particles comprising the functional group-containing fluorine-containing ethylenic polymer may have a core / shell structure.
  • the core / shell type structure for example, the core portion comprises a polymer chain obtained by polymerizing the above-mentioned functional group-free fluorine-containing ethylenic monomer (b), and the shell portion contains the above-mentioned functional group-containing monomer.
  • Particles comprising a polymer chain obtained by copolymerizing the fluoroethylenic monomer (a) and the functional group-free fluorinated ethylenic monomer (b) may be used.
  • the monomer component of the core portion preferably does not contain the above-mentioned functional group-containing fluorine-containing ethylenic monomer (a).
  • the functional group By introducing the functional group only into the shell portion in this manner, the amount of the functional group-containing fluorinated ethylenic monomer (a) can be reduced, which is economical.
  • the shell portion is used in order to have compatibility with a fluorine-containing resin in a fluorine-containing resin molded article described later.
  • a functional group-containing fluorine-containing ethylenic polymer having a particle structure different from that of the core Z-shell type functional group-containing fluorine-containing polymer having a functional group may be used.
  • Those having a core / shell type structure are disclosed in, for example, Japanese Patent Application Laid-Open Nos. Hei 4-154842 and Hei 5-279797. It can be obtained by seed polymerization using a method.
  • the above-mentioned brayer layer is preferably formed by applying a dispersion a component, and the above-mentioned dispersion composition is obtained by dispersing particles comprising the above functional group-containing fluorine-containing ethylenic polymer. is there.
  • the “coating” refers to, as described later, applying the above-described dispersion composition to a substrate, drying if necessary, and then decomposing and generating a liquid medium in the above-described dispersion composition or heating. This means heating so that things can be volatilized.
  • the dispersion composition is not particularly limited as long as the particles comprising the functional group-containing fluorine-containing ethylenic polymer are used as the dispersoid and the liquid medium is used as the dispersion medium.
  • the functional group-containing fluorine-containing ethylenic polymer is used. It may be directly obtained by emulsion polymerization for obtaining a coalescence, or may be a coating composition comprising the above functional group-containing fluorinated ethylenic polymer.
  • the dispersion composition is characterized in that the functional group-containing fluorine-containing ethylenic 2003/010113
  • a surfactant is contained. It may be.
  • the liquid medium is not particularly limited as long as it is generally used as a dispersion medium, but a liquid medium containing water or a water-soluble solvent is preferable from the viewpoint of environmental problems and the like.
  • the water-soluble solvent is a water-soluble organic solvent.
  • the liquid medium is more preferably a mixture of water and a water-soluble solvent, or water.
  • the average particle diameter of the particles comprising the above functional group-containing fluorine-containing ethylenic polymer is usually 5 ⁇ ! 10 / m. If the average particle size of the particles is too large, the dispersibility in the dispersion composition tends to deteriorate, and if the average particle size is too small, it becomes difficult to prepare industrially. Regarding the average particle size of the particles, a more preferred lower limit is 10 nm, a more preferred upper limit is 5 ⁇ , a more preferred upper limit is 1 / ⁇ m, a most preferred upper limit is 300 nm, and a particularly preferred upper limit is It is 150 nm.
  • the functional group of the functional group-containing fluorine-containing ethylenic polymer is oriented to the side closer to the base material, and Since the main chain of the hydrophilic polymer is presumed to be oriented to the side far from the substrate, that is, to the side to which the fluororesin molded article described below is applied, the functional group of the functional group-containing fluorinated ethylene-based polymer has It can contribute to the adhesion between the material and the primer layer, and the fluorine-containing resin in the fluorine-containing resin molded article is compatible with the main chain of the functional group-containing fluorine-containing ethylenic polymer, thereby forming the fluorine-containing resin. It can contribute to the body being bonded to the above-mentioned bramer layer to form a molded body layer.
  • the primer layer is formed by coating a dispersion composition of particles comprising a functional group-containing fluorinated ethylene polymer.
  • the composition may be formed by applying a composition containing an alkoxysilane monomer polymer or a composition containing an alkoxysilane monomer polymer and an organic titanate compound.
  • the above alkoxysilane monomer polymer is a polycondensation of an alkoxysilane monomer.
  • they are disclosed in Japanese Patent Application Laid-Open Nos. Sho 51-32626, Japanese Patent Publication No. Hei 11-37773, Japanese Patent Publication No. Hei 5-131313, etc. Can be used.
  • the alkoxysilane monomer one or more kinds may be used.
  • the primer layer is formed by coating a dispersion composition of particles of a functional group-containing fluorinated ethylene polymer. It is preferable that the composition is formed by coating a composition comprising a fluororesin and a heat-resistant resin other than the fluororesin.
  • the fluororesin used for the primer layer does not have a functional group.
  • the fluororesin used for the primer layer may be the same as or different from the fluororesin used for the fluororesin molded article described later, but from the viewpoint of improving adhesiveness, the fluororesin molded article is preferred. It is preferable that the resin has the same or similar composition as that of the fluorine-containing resin.
  • the fluororesin used for the primer layer is conceptually distinguished from the functional group-containing fluorine-containing ethylenic polymer in that it has no functional group, and the fluorine-containing resin is included in the primer layer. It is conceptually distinguished from the fluorine-containing resin used for the resin molded article.
  • the heat-resistant resin other than the above-mentioned fluororesin may be the same or different from the heat-resistant resin used for the above-mentioned base material, but may be the same or similar from the viewpoint of improving the adhesiveness. preferable.
  • the molded body layer is formed from a fluorinated resin molded body made of a fluorinated resin.
  • the above-mentioned molded article layer is a layer obtained by applying the above-mentioned fluorinated resin molded article on the above-mentioned primer layer and heating it together with the above-mentioned primer layer to adhere to the above-mentioned primer layer.
  • the above-mentioned molded body layer may be a single layer as long as it is formed from a fluorine-containing resin molded body, or may be two or more layers made of different types of fluorine-containing resin molded bodies.
  • the fluorinated resin is made of a fluorinated polymer.
  • the fluorine-containing polymer is not particularly limited as long as it has a fluorine atom.
  • a tetrafluoroethylene-based polymer obtained by polymerizing tetrafluoroethylene [TFE] at least Trifluoro obtained by polymerizing Examples thereof include an ethylene-based polymer and a vinylidene fluoride-based polymer obtained by polymerizing at least vinylidene fluoride.
  • Examples of the above tetrafluoroethylene-based polymer include polytetrafluoroethylene, tetrafluoroethylene noperfluoro (alkyl biel ether) copolymer, and tetrafluoroethylene hexafluoropropylene copolymer. And a copolymer of tetrafluoroethylene / perfluoro (alkylbutyl ether) / hexafluoropropylene and a copolymer of tetrafluoroethylene and ethylene.
  • Examples of the chlorotrifluoroethylene-based polymer include polychloromouth trifluoroethylene, cyclomouth trifluoroethylene-ethylene copolymer, and the like.
  • the above-mentioned vinylidene fluoride polymer examples include polyvinylidene fluoride and the like.
  • the fluororesin may be composed of one or more of these fluoropolymers.
  • the fluororesin is preferably composed of the tetrafluoroethylene-based polymer from the viewpoint of non-adhesiveness, but a resin composed of polytetrafluoroethylene may have poor moldability.
  • the fluororesin is preferably made of a tetrafluoroethylene Z-perfluoro (alkyl vinyl ether) copolymer in view of heat resistance and moldability.
  • some or all of unstable terminal groups such as one COOH, one COOCH 3 , one CH 2 OH derived from a polymerization initiator, a molecular weight regulator and the like are replaced by one CF 3 , —CONH 2 May be substituted by a stable terminal group such as
  • the unstable terminal groups can usually contribute to adhesion with other layers.
  • the fluoropolymer since the fluoropolymer has compatibility with the main chain of the functional group-containing ethylenic polymer described above without having the unstable terminal group, the fluoropolymer has good compatibility with the primer layer. Can be adhered to.
  • foaming may occur when the fluororesin molded article is molded, but foaming can be prevented by not having the above-mentioned unstable terminal group.
  • the term "derived from the polymerization initiator or the molecular weight regulator" refers to the case where the functional group introduced directly by the polymerization initiator or the molecular weight regulator or the like is converted by the polymerization initiator or the molecular weight regulator or the like. Means that it was introduced indirectly.
  • the fluorine-containing resin may further include a conductive filter as long as the object of the present invention is not impaired. It may be used together with one or other additives.
  • the conductive filler include carbon black, grafted carbon black, and an organic conductive agent.
  • the conductive filler is generally used in a proportion of 10% by mass or less based on the mass of the fluororesin.
  • the fluorinated resin molded article is not particularly limited as long as it is obtained by molding the fluorinated resin.However, the fluorinated resin molded article is obtained by molding the fluorinated resin into a cylindrical shape by a usual melt extrusion molding method. Is preferred.
  • the ordinary melt extrusion molding method is not particularly limited, and examples thereof include a method of molding using a general extruder or the like. In the present specification, a molded product obtained by molding into the above “cylindrical shape” is sometimes referred to as a “tube”.
  • the fluorine-containing resin molded body may be one having a surface in contact with the primer layer subjected to an etching treatment or not having been subjected to an etching treatment, but is preferably not one having been subjected to an etching treatment.
  • the primer layer as described above, it is presumed that the main chain of the functional group-containing fluorine-containing ethylenic polymer is oriented to the side to which the fluorine-containing resin molded body is applied.
  • the fluororesin used for the fluororesin molded article has compatibility with the main chain of the functional group-containing fluorinated ethylenic polymer forming the primer layer, and the primer layer and the fluororesin molded article are compatible with each other. Since good adhesive strength can be obtained by heating, the above-mentioned fluorine-containing resin molded article does not have to be etched, and it is preferable that it is not etched in terms of workability and the like.
  • the above-mentioned fluorine-containing resin molded article may be uniaxially or biaxially stretched as required, or may not be stretched.
  • the above-mentioned fluorine-containing resin molded article may have heat shrinkage or may not have heat shrinkage.
  • As the above-mentioned fluorinated resin molded article when the fluorinated resin molded article has heat shrinkability, for example, at 300 ° C. for 3 minutes or more, 1% or more in the axial direction and 25% or less in the circumferential direction
  • the preferred lower limit of the heat shrinkage in the axial direction is 1%, the more preferred lower limit is 0%, and the more preferred upper limit is 5%.
  • the molded article layer is formed by applying a fluororesin molded article on the primer layer and heating the fluororesin molded article to adhere to the primer layer.
  • applying means that a fluororesin molded article is brought into contact with the primer layer.
  • adhing means that the fluorine-containing resin molded article and the primer layer are fused by heating.
  • state of “adhesion” means that after applying a fluororesin molded article on a primer layer and bringing it into contact, the primer layer and the fluororesin molded article are fused by heating. This is a concept that does not include the state before it is made to occur.
  • the “molded body layer” is bonded to one layer of the primer, whereas the “fluorinated resin molded body” may be in a state of being in contact with one layer of the primer.
  • the two are conceptually different in that they are not yet in a bonded state.
  • the temperature at which the primer layer and the fluororesin molded article are heated is not particularly limited as long as the primer layer and the fluororesin molded article can be adhered to each other.
  • the temperature is preferably higher than the higher one of the melting points of the ethylenic polymer, and is lower than the lower one of the decomposition temperature of the fluororesin or the decomposition temperature of the functional group-containing fluoropolymer. I like it.
  • the temperature at which the primer layer and the fluororesin molded body are heated is from 300 to 400 ° C. ° C. A more preferred lower limit is 320 ° C, and a more preferred upper limit is 350 ° C.
  • the time for heating the primer layer and the fluororesin molded body is preferably from 1 to 60 minutes, more preferably 5 minutes, and more preferably 40 minutes.
  • the obtained fluorine-containing laminate is used as a roll for office automation equipment, a belt for office automation equipment or a film for office automation equipment described below, the obtained fluorine-containing laminate is in the range of 10 to 150 / m. It is preferably a thickness. A more preferred lower limit is 20 ⁇ , and a more preferred upper limit is 70 ⁇ m.
  • the functional group of the functional group-containing fluorinated ethylenic polymer constituting the primer layer is oriented to a side close to the substrate. Therefore, the adhesion between the substrate and the primer layer is good.
  • the main chain of the functional group-containing fluorinated ethylenic polymer forming the primer layer is oriented on the side closer to the fluorinated resin molded article. Since the main chain of the functional group-containing fluorinated ethylenic polymer and the fluorinated resin are compatible, the adhesion between the primer layer and the molded article layer is good.
  • the method for producing a fluorinated laminate of the present invention comprises the steps of: forming a primer layer on a substrate; applying a fluorinated resin molded article on the primer layer; and the primer layer and the fluorinated resin molded article. Is heated and adhered.
  • a method for forming a primer layer on the substrate for example, a dispersion composition of particles comprising the functional group-containing fluorine-containing ethylenic polymer described above is coated on a substrate, dried if desired, and then dried. Examples of the method include a method of heating so as to volatilize a liquid medium in the dispersion composition, decomposition products generated by heating, and the like.
  • the method for producing a fluorine-containing laminate of the present invention comprises forming one layer of the primer on the substrate, compared to a conventional production method in which the inner surface of a tube made of fluororesin is coated with a primer. Very easy to handle.
  • the coating method is not particularly limited, and includes, for example, spray coating, roll coating, coating with a doctor blade, dip (dipping) coating, impregnation coating, spin flow coating, curtain flow coating, and the like. Pore coating is preferred.
  • a dispersion composition of particles comprising the functional group-containing fluorinated ethylenic polymer is applied, dried if desired, and then dried.
  • the heating may be carried out so as to volatilize the liquid medium or decomposition products generated by heating, or may not be heated, but the heating causes the decomposition of the liquid medium in the dispersion composition or the heating caused by heating. It is preferable to volatilize products and the like in advance.
  • the fluororesin used for the fluororesin molded article is a tetrafluoroethylene_ / perfluoro (alkyl vinyl ether) copolymer
  • the heating time in the step of forming the primer layer on the substrate is preferably 1 to 30 minutes.
  • the resulting primer layer preferably has a thickness of 1 to 20.
  • the method for producing a fluorinated laminate of the present invention is a method in which a sufficient adhesive force can be obtained without performing an etching treatment.However, in order to further improve the adhesive force, the fluorinated resin molded article is formed on the primer layer. In the step of applying, an etching process or the like may be performed as long as the workability is not impaired.
  • the heating temperature and time in the step of heating and bonding the primer layer and the fluorine-containing resin molded article to each other are the same as those described above for the molded article layer.
  • the above-described method for producing a fluorine-containing laminate can provide a fluorine-containing laminate having good adhesion between the substrate and the primer layer and between the primer layer and the molded body layer without performing the etching treatment. it can. Since the above-mentioned method for producing a fluorine-containing laminate uses a fluorine-containing resin molded product, a fluorine-containing laminate having more excellent wear resistance than a laminate obtained by using a coating method is obtained. Obtainable.
  • the fluorine-containing laminate obtained by the above-mentioned method for producing a fluorine-containing laminate is also one aspect of the present invention.
  • the use of the above-mentioned fluorine-containing laminate is not particularly limited, but it can be suitably used, for example, for office automation equipment (hereinafter, also referred to as “apparatus equipment”).
  • the OA equipment include an image forming apparatus such as a printing machine and a copying machine.
  • the above-described image forming apparatus is an apparatus for forming an image by placing charged toner particles on a transfer material such as paper and fixing unfixed toner particles on the transfer material using a fixing device.
  • the fluorine-containing laminate can be suitably used as a fixing device member used in the fixing device.
  • the fixing device member include a roll for OA equipment, a belt for OA equipment, and a film for ⁇ A equipment.
  • the “0 A device belt” may also be referred to as the “OA device film”.
  • Examples of the roll for OA equipment, the belt for ⁇ A equipment or the film for OA equipment include, for example, a fixing roll, a fixing belt or a fixing film, a pressing roll, and a pressing roll. Examples include a belt and a pressure film.
  • the fixing roll, the fixing belt or the fixing film may be collectively referred to as a “fixing member”.
  • the above-mentioned press roll, press belt or press film may be collectively referred to as a “press member”.
  • the fixing device member normally holds a transfer material such as paper on which unfixed toner is placed between a pressing member and a fixing member, and presses the transfer material against the fixing member by the pressing member.
  • the unfixed toner is melted by heat conduction from the heated fixing member and is fixed on the transfer material. Therefore, the surface of the fixing device member has non-adhesiveness to the toner, heat resistance to the heating of the toner, and abrasion resistance to the pressure contact with the transfer material. It is necessary.
  • the fluorine-containing laminate of the present invention has a molded body layer made of a fluorine-containing resin on its surface, it has excellent non-adhesiveness, heat resistance, abrasion resistance, etc., and is preferably used for the fixing device member. Can be.
  • the fluorine-containing laminate is preferably a roll for an OA device, a belt for an OA device, or a film for an OA device.
  • a primer layer 2 is formed on a substrate 1, and a molded layer 3 is formed on the primer layer 2. And the like having a laminated structure in which is formed.
  • the substrate 1 may be a cored bar or a cored bar coated with silicone rubber.
  • Each of the primer layers 2 and Z or the molded article layer 3 may be a single layer, or may be composed of two or more layers.
  • the fluorine-containing laminate is a belt for OA equipment or a film for OA equipment
  • examples thereof include those having a laminate structure similar to that shown in the schematic cross-sectional view of FIG.
  • the substrate may be a heat-resistant resin or metal belt-like or film-like substrate, or a heat-resistant resin or metal belt-like or film-like substrate coated with silicone rubber. You may.
  • Each of the primer layer and / or the molded article layer may be a single layer, or may be composed of two or more layers.
  • the above-mentioned fluorine-containing laminate has a molded body layer made of the above-mentioned fluorine-containing resin on its surface, it is excellent in non-adhesiveness, heat resistance and abrasion resistance. Alternatively, it can be suitably used for films for OA equipment. Office automation equipment having the above-mentioned fluorine-containing laminate is also one of the present invention.
  • TFE tetrafluoroethylene
  • the concentration of the functional group-containing fluorinated ethylenic polymer in the obtained dispersion composition was 10.9% by weight, and was measured by a dynamic light scattering method using a laser particle size analyzer LPA-3000 (manufactured by Otsuka Electronics).
  • the particle size was 70.7 nm.
  • Tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer CPFA] (AP-230, manufactured by Daikin Industries, Ltd .; melt flow rate [MFR]: 2 g / 10 minutes) and an extruder (manufactured by Tanabe Plastics)
  • MFR melt flow rate
  • Tanabe Plastics an extruder
  • the mixture was extruded into a cylinder by using a resin to obtain a fluororesin molded article having a thickness of 50 ⁇ m.
  • the above-mentioned tubular fluorine-containing resin molded product is also referred to as “PFA tube”.
  • Example 1 Production of roll for OA equipment coated with PFA tube
  • a roll composed of an aluminum core covered with silicone rubber (hereinafter also referred to as a “silicone rubber roll”) was prepared by dispersing particles of a functional group-containing fluoroethylenic polymer prepared by the procedure of Production Example 1.
  • the product was spray-coated, dried at 80-100 ° C for 15 minutes, and further heated at 250 for 10 minutes to form a primer layer.
  • the PFA tube prepared according to the procedure of Production Example 2 was applied on the obtained primer layer, and heated at 340 ° C for 30 minutes to obtain a PFA tube-coated OA equipment portal.
  • the following evaluation was performed on the obtained roll for PFA tube-coated ⁇ A equipment. Table 1 shows the results. (Evaluation)
  • PFA tube coating A 1 cm wide cut is made in the surface of the roll for OA equipment in the direction perpendicular to the axis of the roll, and the molded body layer and the silicone rubber roll are forcibly peeled at a part of the cut, and the peeled part is removed.
  • the spring was fixed to the test holder.
  • PFA tube coating Heat the roll surface for OA equipment to 200 ° C, install the PFA tube coating OA equipment port so that it can rotate, and form the spring away from the PFA tube coating OA equipment port.
  • the load measured by peeling the body layer and the silicone rubber roll was used as a measure of the adhesiveness between the molded body layer and the silicone rubber roll.
  • the inner surface of the PFA tube prepared by the procedure of Production Example 2 was subjected to a chemical etching treatment using a treatment solution mainly containing a sodium-naphthalene complex, and the obtained fluororesin tube was applied to a silicone rubber roll. Then, by heating and bonding at 150 ° C. for 15 minutes, a roll coated with a fluororesin tube was obtained. The obtained fluororesin tube-coated roll was evaluated in accordance with the procedure of Example 1, and the results are shown in Table 1.
  • Comparative Example 2 After spray-coating the dispersion composition of particles comprising the functional group-containing fluorinated ethylenic polymer prepared by the procedure of Production Example 1 on a silicone rubber wool, dried at 80 to 100 ° C for 15 minutes, and further dried. Heating was performed at 250 ° C for 10 minutes to form a primer layer.
  • a 1 cm wide cut is made on the surface of the OA equipment belt, and the molded body layer and the polyimide belt are forcibly peeled off at a part of the cut.
  • Fixed to. Heat the PFA tube-coated OA equipment belt surface to 200 ° C, separate the spring layer from the PFA tube-coated OA equipment belt, and separate the molded body layer from the polyimide belt. It was a measure of the adhesiveness between the polymer and the polyimide belt.
  • the inner surface of the PFA tube prepared by the procedure of Production Example 2 was subjected to a chemical etching treatment using a treatment solution mainly containing a sodium pernaphthalene complex, and the obtained fluororesin tube was applied to a polyimide belt. Then, by heating and bonding at 150 ° C. for 15 minutes, a fluororesin tube-coated belt was obtained.
  • the obtained fluororesin tube-coated belt was evaluated by the procedure of Example 3, and the results are shown in Table 1. Comparative Example 4
  • the fluorinated laminates of Examples 1 and 2 obtained by forming a primer layer using a functional group-containing fluorinated ethylenic polymer had a bimer layer formed thereon.
  • the laminates of Comparative Example 1 and Comparative Example 3 obtained by performing the etching treatment the same or better adhesiveness and abrasion resistance were exhibited.
  • the fluorinated laminates of Example 1 and Example 2 obtained using the fluorinated resin molded article had higher abrasion resistance than the laminates of Comparative Example 2 and Comparative Example 4 obtained using the paint. Was excellent. Industrial applicability
  • the fluorinated laminate of the present invention Since the fluorinated laminate of the present invention has the above-described configuration, it is a fluorinated laminate having good adhesion even without performing an etching treatment and having excellent durability and abrasion resistance.
  • the fluorine-containing laminate of the present invention can be suitably used for office automation equipment and the like.

Landscapes

  • Laminated Bodies (AREA)

Abstract

L'invention concerne un laminé de fluororésine présentant une excellente adhérence malgré un procédé de production sans gravure, et un procédé de production dudit laminé. Le laminé de fluororésine comprend un substrat, une couche primaire formée sur le substrat, et une couche de moulage formée sur la couche primaire, se caractérisant en ce que la surface du substrat sur laquelle est formée la couche primaire est faite d'un caoutchouc résistant à la chaleur, d'une résine résistant à la chaleur, ou d'un métal, que la couche primaire est faite d'un polymère éthylénique contenant du fluor comprenant des groupes fonctionnels, et que la couche de moulage est faite d'un moulage de fluororésine.
PCT/JP2003/010113 2002-08-21 2003-08-08 Lamine de fluororesine et procede de production WO2004018201A1 (fr)

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WO2008126915A1 (fr) * 2007-04-11 2008-10-23 Sumitomo Electric Fine Polymer, Inc. Rouleau de fixation/courroie de fixation, et procédé de fabrication de ceux-ci
WO2012029380A1 (fr) * 2010-08-31 2012-03-08 住友電気工業株式会社 Courroie de fixation
JP2012183378A (ja) * 2005-03-25 2012-09-27 Nipro Corp 凍結保存容器の包装体およびその製造方法
JP5090902B2 (ja) * 2005-03-25 2012-12-05 ニプロ株式会社 凍結保存容器およびその製造方法
WO2015033963A1 (fr) 2013-09-03 2015-03-12 Nok株式会社 Stratifié en caoutchouc de silicone-résine de fluor
CN109789443A (zh) * 2016-10-12 2019-05-21 Ａｇｃ株式会社 层叠体及其制造方法
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WO2005119071A1 (fr) * 2004-06-02 2005-12-15 Junkosha Inc. Couverture de rouleau et procédé de fabrication de rouleau comprenant la couverture de rouleau
CN100432859C (zh) * 2004-06-02 2008-11-12 株式会社润工社 辊包覆物以及含该辊包覆物的辊的制造方法
JP4558381B2 (ja) * 2004-06-02 2010-10-06 株式会社潤工社 ロールの製造方法
JP2005344806A (ja) * 2004-06-02 2005-12-15 Junkosha Co Ltd ロールカバー及び該ロールカバーを含むロールの製造方法
JP5090902B2 (ja) * 2005-03-25 2012-12-05 ニプロ株式会社 凍結保存容器およびその製造方法
US8375688B2 (en) 2005-03-25 2013-02-19 Nipro Corporation Package of freeze storage container and process for producing the same
JP2012236035A (ja) * 2005-03-25 2012-12-06 Nipro Corp 凍結保存容器およびその製造方法
JP2012183378A (ja) * 2005-03-25 2012-09-27 Nipro Corp 凍結保存容器の包装体およびその製造方法
JP5090903B2 (ja) * 2005-03-25 2012-12-05 ニプロ株式会社 凍結保存容器の包装体およびその製造方法
JP4798589B2 (ja) * 2007-04-11 2011-10-19 住友電工ファインポリマー株式会社 定着ローラ・定着ベルトの製造方法
WO2008126915A1 (fr) * 2007-04-11 2008-10-23 Sumitomo Electric Fine Polymer, Inc. Rouleau de fixation/courroie de fixation, et procédé de fabrication de ceux-ci
US8498564B2 (en) 2007-04-11 2013-07-30 Sumitomo Electric Fine Polymer, Inc. Fixing roller/fixing belt, and process for manufacturing the same
KR101390203B1 (ko) * 2007-04-11 2014-04-29 스미토모덴코파인폴리머 가부시키가이샤 정착 롤러 또는 정착 벨트의 제조 방법
WO2012029380A1 (fr) * 2010-08-31 2012-03-08 住友電気工業株式会社 Courroie de fixation
JP5192084B2 (ja) * 2010-08-31 2013-05-08 住友電気工業株式会社 定着ベルト
US9588470B2 (en) 2010-08-31 2017-03-07 Sumitomo Electric Industries, Ltd. Fixing belt
WO2015033963A1 (fr) 2013-09-03 2015-03-12 Nok株式会社 Stratifié en caoutchouc de silicone-résine de fluor
US10025246B2 (en) 2013-09-03 2018-07-17 Nok Corporation Silicone rubber-fluororesin laminate
US10967613B2 (en) 2014-10-31 2021-04-06 Shindo Co., Ltd. Laminate sheet and manufacturing method therefor
CN109789443A (zh) * 2016-10-12 2019-05-21 Ａｇｃ株式会社 层叠体及其制造方法
CN109789443B (zh) * 2016-10-12 2022-05-03 Ａｇｃ株式会社 层叠体及其制造方法

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