WO2012070401A1 - シート状記録材剥離用摺動部材、自動車用シールリング、並びに、産業ガス圧縮機用シールリング及び摺動部材 - Google Patents
シート状記録材剥離用摺動部材、自動車用シールリング、並びに、産業ガス圧縮機用シールリング及び摺動部材 Download PDFInfo
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- WO2012070401A1 WO2012070401A1 PCT/JP2011/075997 JP2011075997W WO2012070401A1 WO 2012070401 A1 WO2012070401 A1 WO 2012070401A1 JP 2011075997 W JP2011075997 W JP 2011075997W WO 2012070401 A1 WO2012070401 A1 WO 2012070401A1
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- sliding member
- resin
- seal ring
- sheet
- recording material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65H—HANDLING THIN OR FILAMENTARY MATERIAL, e.g. SHEETS, WEBS, CABLES
- B65H29/00—Delivering or advancing articles from machines; Advancing articles to or into piles
- B65H29/54—Article strippers, e.g. for stripping from advancing elements
- B65H29/56—Article strippers, e.g. for stripping from advancing elements for stripping from elements or machines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C08L27/18—Homopolymers or copolymers or tetrafluoroethene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F04—POSITIVE - DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS FOR LIQUIDS OR ELASTIC FLUIDS
- F04B—POSITIVE-DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS
- F04B39/00—Component parts, details, or accessories, of pumps or pumping systems specially adapted for elastic fluids, not otherwise provided for in, or of interest apart from, groups F04B25/00 - F04B37/00
- F04B39/0005—Component parts, details, or accessories, of pumps or pumping systems specially adapted for elastic fluids, not otherwise provided for in, or of interest apart from, groups F04B25/00 - F04B37/00 adaptations of pistons
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F04—POSITIVE - DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS FOR LIQUIDS OR ELASTIC FLUIDS
- F04B—POSITIVE-DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS
- F04B39/00—Component parts, details, or accessories, of pumps or pumping systems specially adapted for elastic fluids, not otherwise provided for in, or of interest apart from, groups F04B25/00 - F04B37/00
- F04B39/04—Measures to avoid lubricant contaminating the pumped fluid
- F04B39/041—Measures to avoid lubricant contaminating the pumped fluid sealing for a reciprocating rod
- F04B39/042—Measures to avoid lubricant contaminating the pumped fluid sealing for a reciprocating rod sealing being provided on the piston
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F04—POSITIVE - DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS FOR LIQUIDS OR ELASTIC FLUIDS
- F04B—POSITIVE-DISPLACEMENT MACHINES FOR LIQUIDS; PUMPS
- F04B53/00—Component parts, details or accessories not provided for in, or of interest apart from, groups F04B1/00 - F04B23/00 or F04B39/00 - F04B47/00
- F04B53/14—Pistons, piston-rods or piston-rod connections
- F04B53/143—Sealing provided on the piston
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
- F16J—PISTONS; CYLINDERS; SEALINGS
- F16J9/00—Piston-rings, e.g. non-metallic piston-rings, seats therefor; Ring sealings of similar construction
- F16J9/26—Piston-rings, e.g. non-metallic piston-rings, seats therefor; Ring sealings of similar construction characterised by the use of particular materials
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- 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
- G03G15/2017—Structural details of the fixing unit in general, e.g. cooling means, heat shielding means
- G03G15/2028—Structural details of the fixing unit in general, e.g. cooling means, heat shielding means with means for handling the copy material in the fixing nip, e.g. introduction guides, stripping means
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- 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
- G03G15/65—Apparatus which relate to the handling of copy material
- G03G15/6555—Handling of sheet copy material taking place in a specific part of the copy material feeding path
- G03G15/657—Feeding path after the transfer point and up to the fixing point, e.g. guides and feeding means for handling copy material carrying an unfused toner image
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65H—HANDLING THIN OR FILAMENTARY MATERIAL, e.g. SHEETS, WEBS, CABLES
- B65H2401/00—Materials used for the handling apparatus or parts thereof; Properties thereof
- B65H2401/10—Materials
- B65H2401/11—Polymer compositions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
- F05C—INDEXING SCHEME RELATING TO MATERIALS, MATERIAL PROPERTIES OR MATERIAL CHARACTERISTICS FOR MACHINES, ENGINES OR PUMPS OTHER THAN NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES
- F05C2225/00—Synthetic polymers, e.g. plastics; Rubber
- F05C2225/10—Polyimides, e.g. Aurum
Definitions
- the present invention relates to a sheet-like recording material peeling sliding member, an automobile seal ring, an industrial gas compressor seal ring, and a sliding member.
- the sliding member for peeling the sheet-like recording material is used in, for example, a fixing unit and a developing unit of various image forming apparatuses (hereinafter referred to as “copiers”) using an electrophotographic method such as a copying machine, a laser beam printer, and a printing machine.
- copiers various image forming apparatuses
- it is used as a separation claw or a separation plate for peeling a sheet-like recording material such as copy paper or printing paper from a roll such as a fixing roll.
- the functions of the separation claw and separation plate include non-adhesiveness to which printing toner does not adhere, shape stability that prevents the tip of the separation claw from being deformed or damaged, and a roll that comes into contact with the leading edge.
- Non-aggressive to rolls that do not damage the surface heat resistance that does not deform at a high temperature of about 200 to 250 ° C., especially for separation claws that contact a high-temperature fixing roll, and quietness when sliding with the roll Is required.
- a separation claw for a copying machine in which a non-tacky surface is improved by forming a film mainly composed of a specific fluorocarbon resin such as tetrafluoroethylene on the surface of a polyimide molded body having a specific structure
- Patent Document 1 Separation nail for copying formed by forming a fluororesin fusion coating on the surface of a molded resin composition in which a specific ratio of reinforcing materials such as titanium oxide whisker and zinc oxide whisker is blended with polyetherketone resin (Patent Document) 2) and a separation claw for copying (Patent Document 3) injection-molded with a fluorine-based resin.
- Patent Document 3 in the case of a separation nail for copying that is injection-molded with a fluorine-based resin, an expensive resin such as polyimide is not used and a film is not formed on the surface. Compared with the separation claw for copying described in 1 and 2, the cost and environmental load are improved. However, in the case of a separation claw for copying that is injection-molded with a fluorine-based resin, there are problems of high wear and low rigidity at high temperatures.
- sealing members other than those for peeling seal rings and sheet-shaped recording materials need to seal liquids and gases in transport equipment such as automobiles, office equipment, gas compressors, and other industrial machines. It is used for certain parts and sliding parts. For example, since seal rings used in various pistons for industrial gas compressors and automobiles are also sliding members, it is necessary to have low wear resistance of the seal ring itself and low attack against the mating member of the seal ring. Is done. Furthermore, since this seal ring is also required to have sufficient sealing performance with little gas leakage, it needs to have appropriate flexibility.
- the present filled polytetrafluoroethylene (PTFE) resin material has a limit in mechanical strength (for example, tensile strength and bending strength), and may not be able to cope with it.
- thermoplastic polyimide TPI
- PEEK polyether ether ketone
- high mechanical strength that can withstand high pressure for example, bending strength (30 MPa or more)
- flexibility that satisfies the sealing function for example, bending elastic modulus is 1000 MPa or more, less than 2000 MPa, and It is said that a material having a bending fracture strain of 4% or more, a flexural modulus of 2000 MPa or more and less than 4000 MPa, and a bending fracture strain of 2% or more is required.
- a piston having a specific structure is provided with a functional portion having an outer peripheral surface portion made of a low friction material such as PTFE, PI, and PEEK, and a cylinder inner peripheral surface portion that opposes the outer peripheral surface portion;
- a piston seal structure has been proposed in which the one-side gap is set to 0.03 mm or less (Patent Document 5).
- Patent Document 5 the one-side gap is set to 0.03 mm or less
- the object of the present invention is to have the above functions required as a sheet-like recording material peeling sliding member such as a separation claw and a separation plate, and without forming a film, It is an object of the present invention to provide a sliding member for peeling a sheet-shaped recording material having improved wear resistance and heat-resistant rigidity.
- high mechanical strength for example, bending strength (30 MPa or more)
- flexibility that satisfies the sealing function for example, bending elastic modulus is 1000 MPa or more and less than 2000 MPa, and bending fracture strain is 4%.
- the present inventors have found that the above problems can be solved by using an adhesive fluorocarbon resin and a thermoplastic polyimide, and have completed the present invention. That is, the gist of the present invention is as follows.
- a sheet-shaped recording material peeling sliding member, an automotive seal ring, or an industrial gas compressor seal ring which is made of a resin composition containing 0.5 to 99% by volume of thermoplastic polyimide (C) Or a sliding member.
- the adhesive fluorocarbon resin (A) has at least one functional group selected from the group consisting of an acid anhydride group, a carboxy group, an acid halide group and a carbonate group.
- the sheet-like recording material peeling sliding member, automobile seal ring, or industrial gas compressor seal ring or sliding member according to any one of the above.
- the adhesive fluorocarbon resin (A) is based on a cyclic hydrocarbon monomer having a first repeating unit based on tetrafluoroethylene, a dicarboxylic anhydride group, and a polymerizable unsaturated group in the ring.
- the second repeating unit and a third repeating unit based on other monomers are contained, and the first repeating unit is 50 to 99 with respect to the total molar amount of the first repeating unit, the second repeating unit and the third repeating unit.
- (1) to (4) which is a fluorine-containing copolymer having .89 mol%, the second repeating unit of 0.01 to 5 mol%, and the third repeating unit of 0.1 to 49.99 mol%.
- the adhesive fluorocarbon resin (A) and the fluorocarbon resin (B) are injection-moldable resins, The sliding member for peeling a sheet-like recording material according to any one of (1) to (5), wherein the content of the thermoplastic polyimide (C) is 0.5 to 50% by volume.
- the resin composition contains 0.1 to 30% by volume of at least one selected from the group consisting of a fibrous substance, a whisker-like substance, and a particulate substance as the additive.
- the sheet-like recording material peeling sliding member.
- thermoplastic polyimide (C) 10 ⁇ m or less.
- thermoplastic polyimide (C) The automotive seal ring or the industrial gas compressor seal ring or sliding member according to any one of (1) to (5), containing 1 to 99% by volume of the thermoplastic polyimide (C).
- the present invention has the above functions such as non-adhesiveness, shape stability, non-aggressiveness, heat resistance, and quietness, which are required as a sliding member for peeling a sheet-like recording material such as a separation claw or a separation plate.
- a sheet-shaped recording material peeling sliding member with improved wear resistance and heat-resistant rigidity without forming a film.
- high mechanical strength for example, bending strength (30 MPa or more)
- bending elastic modulus is 1000 MPa or more and less than 2000 MPa
- bending fracture strain is 4%.
- the present invention provides an automotive seal ring, an industrial gas compressor seal ring, or a sliding member made of a resin composition having a bending elastic modulus of 2000 MPa or more and less than 4000 MPa and a bending fracture strain of 2% or more. can do.
- the sheet-like recording material peeling slide member, the automotive seal ring, or the industrial gas compressor seal ring or the slide member according to the present invention includes, as a first component, an adhesive fluorocarbon resin (A), or A resin mixture in which the volume ratio (A / B) of the resin (A) to the fluorocarbon resin (B) different from the resin (A) is 5/95 to 99/1 is used as a second component, and thermoplasticity It consists of a resin composition containing 0.5 to 99% by volume of polyimide (C).
- the sliding member is configured using a specific resin composition including a resin mixture having a specific volume ratio of the resin (A) and the resin (B) and a thermoplastic polyimide (C) as the second component. Also good.
- the resin composition (A) or the specific resin mixture is contained in the resin composition, and the content of the thermoplastic polyimide (C) is 0.5 to 99% by volume, as described above. It is possible to provide a sliding member for peeling a sheet-like recording material, an automotive seal ring, or an industrial gas compressor seal ring or sliding member having excellent characteristics. However, when using a resin mixture according to these uses, a suitable sliding member can be obtained by adjusting the composition and the thermoplastic polyimide (C) content in the resin composition.
- the adhesive fluorocarbon resin (A) used in the present invention will be described first, and then the sheet-like recording material peeling slide member, automotive seal ring, or industrial gas compressor seal ring or slide of the present invention. The moving member will be described.
- Adhesive fluorocarbon resin A
- the adhesive fluorocarbon resin (A) (hereinafter sometimes referred to as an adhesive fluororesin) can be used without particular limitation as long as it is compatible with the thermoplastic polyimide (C). It is.
- “adhesiveness” includes compatibility or affinity with resins including thermoplastic polyimide (C), resins other than resin (A), and other materials.
- a fluororesin containing a repeating unit based on tetrafluoroethylene can be preferably used.
- the base fluororesin include tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), and ethylene-tetrafluoro.
- PFA tetrafluoroethylene-perfluoro (alkyl vinyl ether) copolymer
- FEP tetrafluoroethylene-hexafluoropropylene copolymer
- ethylene-tetrafluoro ethylene-tetrafluoro.
- ETFE ethylene copolymer
- CTFE chlorotrifluoroethylene
- Examples of the adhesive fluorocarbon resin (A) include a fluororesin having at least one functional group selected from the group consisting of an acid anhydride group, a carboxyl group, an acid halide group, and a carbonate group.
- a fluororesin having at least one functional group selected from the group consisting of an acid anhydride group, a carboxyl group, an acid halide group, and a carbonate group.
- an unsaturated carboxylic acid anhydride group can be preferably used, and in particular, a dicarboxylic acid anhydride group can be preferably used.
- a bonded dicarboxylic anhydride group can be preferably used.
- the acid anhydride group a repeating unit based on a cyclic hydrocarbon monomer having a polymerizable unsaturated group and a dicarboxylic acid anhydride group in the ring (hereinafter referred to as “cyclic monomer”) can be preferably used.
- the adhesive fluororesin includes, for example, a first repeating unit based on tetrafluoroethylene, a second repeating unit based on a cyclic hydrocarbon monomer having a dicarboxylic anhydride group and having a polymerizable unsaturated group in the ring.
- a fluorine-containing copolymer having a unit and a third repeating unit based on other monomers excluding tetrafluoroethylene and the cyclic hydrocarbon monomer (hereinafter referred to as “addition monomer”) can be preferably used.
- the adhesive fluororesin contains 50 to 99.89 mol% of the first repeating unit with respect to the total molar amount of the first repeating unit, the second repeating unit, and the third repeating unit.
- a fluorine-containing copolymer having the second repeating unit of 0.01 to 5 mol% and the third repeating unit of 0.1 to 49.99 mol% can be preferably used.
- the adhesive fluororesin has heat resistance, chemical resistance, adhesiveness, moldability, Excellent mechanical properties.
- the adhesive fluororesin has a first repeating unit of 60 to 99.45 mol%, a second repeating unit of 0.05 to 3 mol%, and a third repeating unit of 0.5 to 45 mol%. More preferably, the fluorine-containing copolymer is mol%, the first repeating unit is 80 to 98.9 mol%, the second repeating unit is 0.1 to 1 mol%, and the third repeating unit is A fluorine-containing copolymer in which is 1 to 40 mol% is most preferable.
- the cyclic monomer constituting this adhesive fluororesin is a polymerizable having one or more cyclic hydrocarbons consisting of a 5-membered ring or a 6-membered ring, a dicarboxylic anhydride group, and an intra-ring polymerizable unsaturated group. Compounds are preferred.
- cyclic monomer one having a cyclic hydrocarbon having one or more bridged polycyclic hydrocarbons can be preferably used, and in particular, a cyclic hydrocarbon composed of one bridged polycyclic hydrocarbon, two or more Those having a cyclic hydrocarbon condensed with a bridged polycyclic hydrocarbon or a cyclic hydrocarbon condensed with a bridged polycyclic hydrocarbon and another cyclic hydrocarbon can be preferably used.
- cyclic monomer those having an intra-ring polymerizable unsaturated group containing one or more polymerizable unsaturated groups present between carbon atoms constituting the hydrocarbon ring can be preferably used.
- this cyclic monomer a dicarboxylic anhydride group (—CO—O—CO—) bonded to two carbon atoms constituting the hydrocarbon ring or bonded to two carbon atoms outside the ring is used. What has is preferably used.
- examples of the cyclic monomer include 5-norbornene-2,3-dicarboxylic acid anhydride (hereinafter referred to as “NAH”) and acid anhydrides represented by the following formulas (1) to (3).
- Etc. can be preferably used, and NAH can be particularly preferably used.
- an adhesive fluororesin containing a repeating unit composed of the cyclic monomer can be easily produced without using a special polymerization method.
- one containing at least one selected from the group consisting of HFP, CTFE, CF 2 ⁇ CFOR f1 , ethylene and CH 2 ⁇ CX 3 (CF 2 ) q X 4 can be used.
- HFP, CTFE and CF 2 CFOR f1 .
- CF 2 CFOR f1.
- R f1 is preferably a C 1-6 perfluoroalkyl group, more preferably a C 2-4 perfluoroalkyl group, and most preferably a perfluoropropyl group.
- the adhesive fluororesin those having a melting point within the range of 150 to 320 ° C. can be preferably used, and those having the melting point within the range of 200 to 310 ° C. can be preferably used.
- Melting point Adhesive fluororesin in this range has heat resistance such as polyphenylene sulfide (PPS), polyimide (PI), polyether ether ketone (PEEK), liquid crystalline polymer (LCP), semi-aromatic polyamide. It is suitable for melting and kneading a polymer alloy with a super engineering plastic having a temperature of 150 ° C. or higher at a high temperature, and is excellent in melt moldability. Note that the melting point of the adhesive fluororesin can be appropriately adjusted depending on the content ratio of each repeating unit contained in the adhesive fluororesin.
- the first repeating unit based on TFE is 50 to 99.89 mol%
- the second repeating unit is 0.01 to 5 mol%
- the third repeating unit based on CTFE is 0. It is also possible to use a fluororesin that is from 1 to 49.99 mol%.
- the method for producing the adhesive fluororesin is not particularly limited, and a radical polymerization method using a radical polymerization initiator is used.
- Polymerization methods include bulk polymerization, solution polymerization using organic solvents such as fluorinated hydrocarbons, chlorinated hydrocarbons, fluorinated chlorohydrocarbons, alcohols, hydrocarbons, aqueous media, and appropriate organic solvents as required. Suspension polymerization, emulsion polymerization using an aqueous medium and an emulsifier, and solution polymerization is particularly preferable.
- the radical polymerization initiator is preferably a radical polymerization initiator having a half-life of 10 hours and a temperature of 0 ° C. to 100 ° C. More preferably, it is 20 to 90 ° C.
- Specific examples thereof include azo compounds such as azobisisobutyronitrile, non-fluorinated diacyl peroxides such as isobutyryl peroxide, octanoyl peroxide, benzoyl peroxide and lauroyl peroxide, diisopropyl peroxydicarbonate, di-n-propyl.
- Peroxydicarbonates such as peroxydicarbonate, peroxyesters such as tert-butylperoxypivalate, tert-butylperoxyisobutyrate, tert-butylperoxyacetate, (Z (CF 2 ) r COO) 2 (where Z is Inorganic compounds such as fluorine-containing diacyl peroxide, potassium persulfate, sodium persulfate, ammonium persulfate, etc. Product, and the like.
- a chain transfer agent may be used to control the melt flow rate (MFR) of the fluorinated copolymer.
- Chain transfer agents include alcohols such as methanol and ethanol, chlorofluorohydrocarbons such as 1,3-dichloro-1,1,2,2,3-pentafluoropropane, 1,1-dichloro-1-fluoroethane, Hydrocarbons such as pentane, hexane, and cyclohexane are listed.
- Examples of the chain transfer agent for introducing an adhesive functional group to the polymer terminal of the fluorinated copolymer include acetic acid, acetic anhydride, methyl acetate, ethylene glycol, propylene glycol and the like.
- the polymerization conditions for the adhesive fluororesin used in the present invention are not particularly limited, and the polymerization temperature is preferably 0 to 100 ° C, more preferably 20 to 90 ° C.
- the polymerization pressure is preferably from 0.1 to 10 MPa, more preferably from 0.5 to 3 MPa.
- the polymerization time is preferably 1 to 30 hours.
- the adhesive fluororesin obtained by the above production method can be obtained in the form of pellets, powders, or other forms according to a conventional method.
- the sliding member for peeling sheet-like recording material has, as a first component, an adhesive fluorocarbon resin (A) or the resin (A) and the above-mentioned A resin mixture having a volume ratio (A / B) of 5/95 to 99/1 with a fluorocarbon resin (B) different from the resin (A) is used, and thermoplastic polyimide (C) 0.
- the resin composition preferably contains 5 to 50% by volume.
- the sliding member for peeling the sheet-like recording material according to the present invention contains the thermoplastic polyimide (C) at a specific ratio, it has excellent heat resistance and high mechanical strength based on its characteristics. (In other words, it has shape stability and heat resistance) and contains the resin (A) (if necessary, the resin (B)). Therefore, based on the characteristics of the fluorocarbon resin, excellent chemical resistance (that is, (Non-adhesive) and moderate flexibility (ie, quietness). Further, unlike the conventional fusion coating, not only the surface but also the whole is made of the resin composition, so that it is possible to suppress the aggressiveness to the roll.
- the adhesive fluorocarbon resin (A) used in the present invention has an appropriate flexibility, excellent heat resistance, chemical resistance, weather resistance, gas barrier, and the like possessed by the fluorocarbon resin. Since the free energy on the surface is moderately high while having properties such as properties, it becomes possible to constitute a resin composition such as a polymer alloy combined with other materials. Therefore, a resin composition having both excellent properties such as heat resistance and mechanical strength of the thermoplastic polyimide and the excellent properties of the fluorocarbon resin as in the present invention can be obtained.
- the fluorocarbon resin (B) is not particularly limited as long as it is a fluorocarbon resin other than the adhesive fluorocarbon resin (A). It is possible to use a known injection-moldable fluorocarbon-based resin, for example, one selected from the group consisting of PFA, FEP, ETFE, CTFE-TFE copolymer and the like alone or a blend of two or more. it can.
- the resin mixture has a volume ratio (A / B) between the resin (A) and a fluorocarbon resin (B) different from the resin (A) of 5/95 to 99/1, preferably 15 / 85 to 90/10, more preferably 20/80 to 85/15. Thereby, compatibility with thermoplastic polyimide (C) is obtained.
- the volume ratio (A / B) is less than 5/95, desired compatibility tends to be not obtained.
- the volume ratio of the resin mixture is calculated from the mass ratio and specific gravity of each component.
- the resin (A) and the resin (B) constituting the sheet-like recording material peeling sliding member are preferably those that can be injection-molded. Thereby, it becomes possible to more easily manufacture molded articles having various shapes such as a separation claw and a separation plate.
- injectable means that the melt flow rate (MFR) of the resin is 0.2 to 4.0 mm 3 / sec.
- the method for producing the resin mixture is not particularly limited, and a general method used for mixing resins, for example, biaxial kneading, dry blending of powder, and the like can be employed.
- thermoplastic polyimide (C) is not particularly limited, and a known one or a commercially available one can be used. Examples of commercially available products include Aurum PD-500 manufactured by Mitsui Chemicals.
- the resin composition preferably contains 0.5 to 50% by volume of the thermoplastic polyimide (C).
- the thermoplastic polyimide (C) is less than 0.5% by volume, the heat-resistant rigidity and wear resistance tend not to be improved.
- the content is more than 50% by volume, the fluidity and surface properties at the time of injection molding. However, non-adhesiveness tends to decrease.
- it may be 0.5 to 30% by volume in consideration of fluidity securing at the time of injection molding, heat resistance rigidity, and wear resistance.
- the thermoplastic polyimide (C) preferably has an average dispersed particle size of 10 ⁇ m or less.
- a thermoplastic polyimide (C) is appropriately dispersed in the resin (A) or the resin mixture, and a sheet-like recording material peeling sliding member with improved wear resistance and heat-resistant rigidity is obtained.
- the average dispersed particle diameter can be measured with a scanning electron microscope.
- the resin composition is at least one selected from the group consisting of a fibrous substance, a whisker-like substance, and a particulate substance (hereinafter, specified) as an additive. It may be referred to as an additive).
- an additive heat-resistant rigidity and abrasion resistance improve. These can be selected as appropriate in consideration of the reinforcing effect, wear resistance, and fluidity during injection molding.
- the fibrous substance examples include inorganic and organic fibrous substances.
- inorganic fibrous materials include metal fibers such as carbon fibers, glass fibers, graphite fibers, and stainless fibers.
- organic fibrous materials include various synthetic fibers and natural fibers. Among these, carbon fibers and organic fibers are preferable from the viewpoints of wear resistance and non-aggression.
- the whisker-like substance is a needle-like (bowl-like) single crystal or polycrystal, and the crystal has a mean diameter of 0.01 to 10 ⁇ m.
- inorganic and organic whisker-like substances can be used.
- the inorganic whisker-like substance for example, calcium silicate whisker, calcium carbonate whisker, calcium sulfate whisker, magnesium sulfate whisker, magnesium nitrate whisker, aluminum borate whisker, titanium oxide whisker, zinc oxide whisker, potassium titanate whisker, Wollast Knight Whisker etc. are mentioned. Of these, calcium carbonate whisker and potassium titanate whisker are preferred from the viewpoints of wear resistance and non-aggression.
- organic or inorganic particulate matter having a particle diameter of 0.5 to 100 ⁇ m can be used.
- examples of the inorganic type include talc, mica, montmorillonite, silica, and calcium carbonate.
- examples of the organic type include aramid powder of wholly aromatic polyamide. Of these, talc and calcium carbonate are preferred from the viewpoints of wear resistance, non-aggression, and cost.
- the content of the additive (specific additive) in the resin composition includes heat resistance rigidity, wear resistance, and fluidity during injection molding. In view of the above, it is preferably 0.1 to 30% by volume, more preferably 3 to 20% by volume.
- additives include mold release agents, lubricants, heat stabilizers, antioxidants, UV absorbers, crystal nucleating agents, foaming agents, rust inhibitors, ion trap agents, flame retardants, flame retardant aids, dyes -One or more kinds of colorants such as pigments and antistatic agents are included.
- the total volume ratio of the resin (A) or the resin mixture, the thermoplastic polyimide (C), and the specific additive. May be configured to be 100% by volume.
- the water contact angle of the surface of the sliding member for peeling the sheet-like recording material according to the present invention is 90 ° or more. In this case, the non-adhesiveness of the toner to the sheet-like recording material peeling sliding member is further improved.
- the method for producing the resin composition used for the sliding member for peeling the sheet-like recording material according to the present invention is not particularly limited, and is a method used for mixing ordinary resins, for example, biaxial kneading, powder Dry blend etc. can be adopted.
- a resin composition it can be set as the general form of resin, such as a pellet, strand, powder, a paste.
- the sliding member for peeling the sheet-like recording material according to the present invention can be obtained by integrally molding the whole by injection molding or the like using the above resin composition. Therefore, the process for forming the fusion coating is not required, and the manufacturing process can be simplified and the environmental load can be reduced as compared with the case where the conventional fusion coating is formed. In addition, since injection molding can be performed, there is an advantage of excellent mass productivity.
- the sheet-like recording material peeling sliding member made of the resin composition as described above is used, for example, in a fixing unit or a developing unit of a copying machine, from a roll such as a fixing roll to a sheet-like recording material such as copying paper or printing paper. It can be suitably used as a sliding member such as a separation claw or separation plate to be peeled off.
- the shape of the separation claw for the copying machine is not particularly limited, and may basically be the same shape as a conventional separation claw.
- the separation claw for a copying machine of the present embodiment is integrally formed of the resin composition as a whole.
- the support shaft 2 is integrally formed with the separation claw 1.
- the separation claw 1a is provided with a shaft hole 2a.
- the separation claw 1 is rotatable about the support shaft 2 with the rotation shaft 11 of the fixing roll or other roll 10 and the support shaft 2 in parallel.
- the separation claw 1a is inserted into the mounting shaft 4 provided in parallel with the rotating shaft 11 of the roll 10 through the shaft hole 2a so as to be rotatable around the mounting shaft 4, and a biasing means 3 such as a spring.
- a biasing means 3 such as a spring.
- the tip angle of the separation claw is preferably in the range of 5 to 80 degrees, A range of 45 degrees is more preferable.
- the tip angle is 5 degrees or less, although depending on the pressing force against the roll, a gap is formed between the roll and the separation claw tip due to the bending deformation, and the paper jam easily occurs when the paper is passed.
- the tip angle is 80 degrees or more, bending deformation is unlikely to occur, but the copy paper separating function is hardly exhibited.
- the automotive seal ring or industrial gas compressor seal ring or sliding member according to the present invention has an adhesive property as a first component.
- the second component is made of a resin composition containing 1 to 99% by volume of thermoplastic polyimide (C).
- the adhesive fluorocarbon resin (A) or the resin mixture and the thermoplastic polyimide (C) a resin composition having appropriate mechanical strength and flexibility can be obtained. It is suitable as a constituent material for automobile seal rings and industrial gas compressor seal rings or sliding members.
- the adhesive fluorocarbon resin used in the automotive seal ring and industrial gas compressor seal ring or sliding member of the present invention has moderate flexibility and mechanical strength,
- the surface free energy is moderately high while having the properties such as excellent heat resistance, chemical resistance, weather resistance, and gas barrier properties of the fluorocarbon resin.
- an alloyed resin composition can be formed. Therefore, the alloyed resin composition obtained by mixing thermoplastic polyimide and adhesive fluorocarbon resin, which will be described later, has excellent characteristics such as heat resistance and mechanical strength of thermoplastic polyimide, and fluorocarbon resin.
- a resin composition having both of the above excellent characteristics can be obtained.
- the fluorocarbon resin (B) used in the automotive seal ring and industrial gas compressor seal ring or sliding member of the present invention may be a fluorocarbon resin other than the adhesive fluorocarbon resin (A).
- a known fluorocarbon-based resin for example, one selected from the group consisting of PFA, FEP, ETFE, CTFE-TFE copolymer and the like alone or a blend of two or more can be used.
- the resin mixture used in the automotive seal ring and the industrial gas compressor seal ring or the sliding member of the present invention comprises the resin (A) and a fluorocarbon resin (B) different from the resin (A).
- the volume ratio (A / B) is 5/95 to 99/1. Moreover, as a minimum of volume ratio (A / B), More preferably, it is 10/90, More preferably, it is 50/50. Thereby, moderate softness
- the volume ratio of the resin mixture is calculated from the mass ratio and specific gravity of each component.
- the method for producing the resin mixture is not particularly limited, and a general method used for mixing resins, for example, biaxial kneading, dry blending of powder, and the like can be employed.
- thermoplastic polyimide (C) is not particularly limited, and a known one or a commercially available one can be used. Examples of commercially available products include Aurum PD-500 manufactured by Mitsui Chemicals.
- the resin composition used in the automotive seal ring and the industrial gas compressor seal ring or the sliding member of the present invention contains 1 to 99% by volume of the thermoplastic polyimide (C).
- the upper limit of the content is preferably 90% by volume, more preferably 80% by volume.
- the lower limit of the content is more preferably 20% by volume, further preferably 40% by volume, and most preferably 60% by volume.
- the resin composition may contain 50% by volume or less of an additive.
- an additive is not particularly limited, and a commonly used resin filler can be used.
- carbon fiber, glass fiber, graphite fiber, metal fiber such as stainless steel fiber, synthetic fiber such as aramid fiber, various whiskers, graphite, molybdenum disulfide and the like can be mentioned. It is also possible to use the specific additive described in the above (b) sliding member for peeling the sheet-like recording material.
- additives other than the above fillers are used in the resin composition as long as the effects of the present invention are not hindered. Also good.
- additives include mold release agents, lubricants, heat stabilizers, antioxidants, UV absorbers, crystal nucleating agents, foaming agents, rust inhibitors, ion trap agents, flame retardants, flame retardant aids, dyes -One or more kinds of colorants such as pigments and antistatic agents are included.
- the resin composition may appropriately contain the additive and the like, but in the resin composition, the resin (A ) Or the volume ratio of the resin mixture, the thermoplastic polyimide (C) and the filler may be 100% by volume. That is, the resin composition contains the resin (A) or the resin mixture, and the thermoplastic polyimide (C) as essential components, and includes the optional filler (the volume ratio of the filler). May be 0.), and other components may not be included. With this configuration, the wear resistance can be improved and the mechanical strength can be improved without losing the appropriate flexibility and low friction property of the resin (A). In addition, a more preferable aspect can be obtained as a seal ring for an industrial gas compressor or a sliding member.
- the resin (A) or the resin mixture, the thermoplastic polyimide (C), In the case of mixing with the filler, there is no particular limitation as long as these can be mixed uniformly. For example, biaxial kneading, dry blending of powders, and the like, are not particularly limited. Etc. can be adopted.
- a resin composition it can be set as the general form of resin, such as a pellet, a strand, powder, a paste, according to a usual method.
- the automotive seal ring, the industrial gas compressor seal ring or the sliding member according to the present invention is made of the above resin composition by using injection molding, transfer molding, compression molding (hot molding method, free baking method, etc.) ) And other general molding methods.
- “seal ring” means a part that seals gas, liquid, solid, powder, etc., such as a piston ring used in an automobile (for example, a car air conditioner compressor) or an industrial gas compressor.
- the “sliding member” means a component that moves (slids) with low friction while receiving a load of a piston, a piston rod, or the like in the vicinity of a piston ring of an industrial gas compressor. Further, when the seal ring is used as a sliding part, the case where the sliding part is used as a seal ring is also within the scope of the present invention.
- the seal ring and sliding member molded as described above have high mechanical strength and moderate flexibility. That is, the bending strength is 30 MPa or more as an index of mechanical strength, the flexural modulus is 1000 MPa or more and less than 2000 MPa, and the bending breaking strain is 4% or more, or the bending elastic modulus is 2000 MPa or more and 4000 MPa as an index of mechanical strength. And the bending fracture strain is 2% or more.
- the automotive seal ring, the industrial gas compressor seal ring or the sliding member of the present invention is a component for sealing a medium such as gas and liquid, It can be suitably used as a part used for a sliding part, and is more suitable as a seal ring of a sliding part.
- Specific examples of seal rings for automobiles or industrial gas compressors according to the present invention include piston rings, rod packings, gland packings, and specific examples of sliding members for industrial gas compressors include lidars. Examples include, but are not limited to, rings and bearings.
- the seal rings for automobiles and industrial gas compressors or sliding members of the present invention they are particularly suitable as seal rings that also have a function as a sliding member for industrial gas compressors that require more airtightness. .
- Adhesive Fluorocarbon Resin A (adhesive fluororesin) was produced using F (perfluoropropyl vinyl ether, manufactured by Asahi Glass Co., Ltd.) (hereinafter referred to as PPVE).
- AK225cb 1,3-dichloro-1,1,2,2,3-pentafluoropropane
- PPVE 1,3-dichloro-1,1,2,2,3-pentafluoropropane
- a polymerization initiator solution a solution in which (perfluorobutyryl) peroxide was dissolved in AK225cb at a concentration of 0.36% by mass was prepared, and 3 L of the solution was added to the polymerization tank at a rate of 6.25 mL per minute. Polymerization was carried out while continuously adding. Further, TFE was continuously charged so that the pressure in the polymerization tank during the polymerization reaction was maintained at 0.89 MPa / G. A solution in which NAH was dissolved in AK225cb at a concentration of 0.3% by mass was continuously charged in an amount corresponding to 0.1 mol% with respect to the number of moles of TFE charged during the polymerization.
- the copolymer composition of this adhesive fluororesin (sometimes abbreviated as m-PFA) is determined to be a repeating unit based on TFE (first repeating unit) / NAH.
- the recurring unit based on (second repeating unit) / the repeating unit based on PPVE (third repeating unit) 97.9 / 0.1 / 2.0 (mol%).
- the adhesive fluororesin (m-PFA) had a melting point of 300 ° C. and a melt flow rate (MFR) of 0.39 mm 3 / sec. Therefore, the obtained m-PFA was injection moldable.
- TPI Product name “AURUM (registered trademark) PD-500”, specific gravity ( ⁇ ) 1.33), additive (specific additive), carbon fiber (specific gravity ( ⁇ ) 1.7), glass fiber (specific gravity ( ⁇ 2.5), a calcium carbonate whisker (specific gravity ( ⁇ ) 2.8) and a resin composition having a volume-based composition shown in Table 1 (Table 2 shows a mass-based composition) According to the twin screw extruder And pellets were obtained. Using the obtained resin composition, a sheet-like recording material peeling sliding member (injection molded product) as an evaluation sample was molded by injection molding according to a conventional method.
- ⁇ Sliding with PFA Evaluation of opponent aggression (non-aggression)> Using the injection-molded product prepared in Examples and the like, the aggressiveness of the injection-molded product against PFA was evaluated by a pin-on-disk friction and wear tester under the conditions shown in Table 4 (however, the temperature of PFA was 25 ° C.). The evaluation criteria are as follows. ⁇ : Damage depth of PFA is 30 ⁇ m or less ⁇ : Damage depth of PFA is larger than 30 ⁇ m and 100 ⁇ m or less
- ⁇ Heat deformation characteristics> Using an injection-molded article prepared in Examples and the like, a load of 1.96 N was applied to an edge portion having a thickness of 2.5 mm, a tip angle of 45 °, and a tip R of 0.05 mm on a 200 ° C. stainless steel disk. By measuring the dimension in the load direction after 2 hours and calculating the dimensional difference (deformation amount) before and after the test, the thermal deformation characteristics were evaluated.
- the evaluation criteria are as follows. A: Deformation amount is less than 0.05 mm B: Deformation amount is 0.05 mm or more and less than 0.15 mm ⁇ : Deformation amount is 0.15 mm or more
- each evaluation criterion is rated as 2 points, ⁇ as 1 point, and ⁇ as 0 point, and the sum of both scores is 3 to 4 points.
- the product cost was evaluated with ⁇ as the product, ⁇ as the 2 points, and ⁇ as the 0-1 points.
- Comparative Example 2 as for the surface appearance of the injection molded product, surface peeling was observed, and in the measurement of the average dispersed particle diameter of TPI, poor dispersion was observed in the SEM image.
- Each dispersion particle size measurement sample was immersed in liquid nitrogen and frozen. The sample was frozen and cut, and the cross section was observed with SEM (S-3400N, manufactured by Hitachi High-Technologies Corporation). Measurements were made using the attached length measurement function.
- the average dispersed particle size is a guideline for judging the compatibility of each component contained in the resin composition. The average dispersed particle size is smaller than that when no m-PFA is contained, and the smaller the size, the better the compatibility.
- ⁇ Bending test> Using an evaluation sample for measuring each physical property, a bending test was performed in accordance with JIS K7203, and bending elastic modulus, bending maximum strength, and bending breaking strain were measured.
- ⁇ Adaptability as automotive seal ring, industrial gas compressor seal ring or sliding member was evaluated based on the results of a bending test.
- the evaluation criteria are as follows. Note that the maximum bending strength was adopted as the bending strength, which is an index of high mechanical strength. Those satisfying the following (i) and (ii) or (iii) were rated as ⁇ , and those not satisfying either (i), (ii) or (iii) were marked as x. (I) The bending maximum strength is 30 MPa or more.
- the flexural modulus is 1000 MPa or more and less than 2000 MPa, and the bending fracture strain is 4% or more.
- the flexural modulus is 2000 MPa or more and less than 4000 MPa, and the bending fracture strain is 2% or more.
- the volume-based composition shown in Table 5 (in Table 6) was prepared by a twin-screw kneading extruder (manufactured by Technobel, KZW15TW-45MG-NH) according to a conventional method, and obtained as pellets.
- the above-mentioned evaluation sample for measuring the average dispersed particle diameter sheet having a thickness of 1 mm
- the above-described evaluation sample for measuring physical properties was formed by transfer molding according to a conventional method.
- Example 12 A resin composition having a volume-based composition shown in Table 5 (Table 6 shows a mass-based composition) was prepared in the same manner as in Example 5, and was subjected to compression molding according to a conventional method to evaluate an evaluation sample for measuring physical properties ( A substantially cylindrical shape having an outer diameter of 60 mm, an inner diameter of 30 mm, and a length of 100 mm).
- PTFE As PTFE, PTFE manufactured by Asahi Glass Co., Ltd. (product name “Fluon (registered trademark) PTFE G165”, specific gravity 2.17) is compression-molded by a free baking method according to a conventional method, and an evaluation sample for measuring physical properties to be described later (Outer diameter ⁇ 60 mm ⁇ inner diameter ⁇ 30 mm ⁇ substantially cylindrical shape with a length of 100 mm) was molded.
- Example 14 to 16, Comparative Example 8 The powder of each component was stirred and mixed by a mixer according to a conventional method so as to have a volume-based composition shown in Table 8 (Table 9 shows a mass-based composition).
- Table 9 shows a mass-based composition.
- the obtained mixture was compression-molded by a hot molding method, and an evaluation sample for measuring physical properties comprising a resin composition having the composition shown in Table 8 (Table 9) (substantially cylindrical shape with outer diameter ⁇ 60 mm ⁇ inner diameter ⁇ 30 mm ⁇ length 100 mm) ).
- CF carbon fiber
- a PAN-based middle fiber specific gravity 1.76) was used.
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Abstract
Description
中でも、シート状記録材剥離用摺動部材は、例えば、複写機、レーザービームプリンター、印刷機等の電子写真方式による各種画像形成装置(以下、「複写機」という)の定着部や現像部において、定着ロール等のロールから複写紙、印刷紙等のシート状記録材を剥離する分離爪や分離板などとして用いられる。
また、ポリイミドなどの成形体の表面にフッ素系樹脂を300℃程度の高温で溶融して被膜を形成させることから、被膜工程が余計に必要となり、また、高温加熱のためのエネルギーが必要になるため、よりコストがかかる上、環境負荷の面からも望ましくないという問題がある。
さらに、ポリイミドなどの樹脂は、一般に表面硬度が高いため、その表面にフッ素系樹脂で被膜を形成したとしても、表面硬度は高く、その最先端部が接触するロール表面を損傷させる危険性があり、加えて、被膜が摩耗したり、何らかの事情により被膜が剥離したりした場合には、著しくロール表面を損傷させるという問題がある。また、被膜表面の硬度が高いため、静音性はあまり良くないとされている。
加えて、基材の表面に被膜を形成してなる分離爪においては、形成された被膜の出来が分離爪の性能を左右するところ、被膜を形成する工程は、最終工程でありながら、最も不良の出やすい工程であるため、有人検査が必要になる。そのため、当該検査を行う管理面でコストがかかるという問題がある。
また、高い圧力に耐えられる高い機械強度(例えば、曲げ強度(30MPa以上))と、シール機能を満足させる柔軟性(例えば、曲げ弾性率が1000MPa以上、2000MPa未満、かつ、曲げ破断歪が4%以上、または、曲げ弾性率が2000MPa以上、4000MPa未満、かつ、曲げ破断歪が2%以上)を持ち合わせた樹脂組成物からなる、自動車用シールリング、又は、産業ガス圧縮機用シールリング若しくは摺動部材を提供することにある。
即ち、本発明の要旨は、以下の通りである。
接着性フルオロカーボン系樹脂(A)、または、
前記樹脂(A)と前記樹脂(A)とは異なるフルオロカーボン系樹脂(B)との容積比(A/B)が5/95~99/1である樹脂混合物を、
第2成分として、熱可塑性ポリイミド(C)0.5~99容積%を含む樹脂組成物からなる、シート状記録材剥離用摺動部材、自動車用シールリング、又は、産業ガス圧縮機用シールリング若しくは摺動部材。
前記熱可塑性ポリイミド(C)の含有量が0.5~50容積%である、前記(1)~(5)のいずれかに記載のシート状記録材剥離用摺動部材。
また、高い圧力に耐えられる高い機械強度(例えば、曲げ強度(30MPa以上))と、シール機能を満足させる柔軟性(例えば、曲げ弾性率が1000MPa以上、2000MPa未満、かつ、曲げ破断歪が4%以上、または、曲げ弾性率が2000MPa以上、4000MPa未満、かつ、曲げ破断歪が2%以上)を持ち合わせた樹脂組成物からなる自動車用シールリング又は産業ガス圧縮機用シールリング若しくは摺動部材を提供することができる。
即ち、本発明では、第1成分としての樹脂(A)および第2成分としての熱可塑性ポリイミド(C)を含む樹脂組成物を用いて摺動部材を構成しても良いし、第1成分としての、樹脂(A)と樹脂(B)との特定容積比の樹脂混合物、および、第2成分としての熱可塑性ポリイミド(C)を含む特定の樹脂組成物を用いて摺動部材を構成しても良い。
前記接着性フルオロカーボン系樹脂(A)(以下、接着性フッ素樹脂と称する場合がある。)としては、熱可塑性ポリイミド(C)と相容性があるものであれば、特に限定なく用いることが可能である。ここで「接着性」には、熱可塑性ポリイミド(C)をはじめとする樹脂、樹脂(A)以外の他の樹脂、その他の材料との相容性ないし親和性があること含む。
本発明に係るシート状記録材剥離用摺動部材は、第1成分として、接着性フルオロカーボン系樹脂(A)、または、前記樹脂(A)と前記樹脂(A)とは異なるフルオロカーボン系樹脂(B)との容積比(A/B)が5/95~99/1である樹脂混合物を含み、第2成分として、熱可塑性ポリイミド(C)0.5~50容積%を含む樹脂組成物からなるのが好ましい。
尚、樹脂混合物の容積比は、各成分の質量比と比重から算出される。
尚、前記の平均分散粒子径は、走査型電子顕微鏡により測定することができる。
本発明に係るシート状記録材剥離用摺動部材では、複写機用分離爪の形状は特に限定されるものではなく、基本的には従来からの分離爪と同様の形状のものでよい。本実施形態の複写機用分離爪は、その全体が前記樹脂組成物により一体に成形されている。例えば、図1に示すように、分離爪1に支軸2が一体に成形してある。または、例えば図2に示すように、分離爪1aに軸孔2aを設けてある。そして、図3に示すように、前記分離爪1は、定着ロールその他のロール10の回転軸11と前記支軸2とを平行にして該支軸2を中心に回動可能とし、また、前記分離爪1aは、前記軸孔2a部分をロール10の回転軸11と平行に設けられた取付軸4へ挿通して、該取付軸4を中心に回動可能とし、バネ等の付勢手段3によりロール10の表面へ爪先端部を適正な圧力で接触させた状態に取り付けられる。
本発明に係る自動車用シールリング又は産業ガス圧縮機用シールリング若しくは摺動部材は、第1成分として、接着性フルオロカーボン系樹脂(A)、または、前記樹脂(A)と前記樹脂(A)とは異なるフルオロカーボン系樹脂(B)との容積比(A/B)が5/95~99/1である樹脂混合物を含み、第2成分として、熱可塑性ポリイミド(C)1~99容積%を含む樹脂組成物からなるのが好ましい。
尚、本発明では、「シールリング」とは、自動車(例えばカーエアコンのコンプレサーなど)や産業ガス圧縮機に用いられるピストンリングなどの気体、液体、固体、粉体などを封止する部品を意味し、「摺動部材」とは、産業ガス圧縮機のピストンリングの近傍で、ピストンやピストンロッドなどの荷重を受けつつ低摩擦で移動(摺動)する部品を意味する。また、シールリングが摺動部品として使用される場合、摺動部品がシールリングとして使用される場合も本発明の範疇である。
本発明に係る自動車用または産業ガス圧縮機用シールリングの具体例としては、ピストンリング、ロッドパッキン、グランドパッキンなどが挙げられ、また、産業ガス圧縮機用摺動部材の具体例としては、ライダリング、軸受などが挙げられるが、これらに限定されるわけではない。
本発明の自動車用シールリングおよび産業ガス圧縮機用シールリングまたは摺動部材の中でも、より気密性が要求される産業ガス圧縮機用の摺動部材としての機能も有するシールリングとして特に好適である。
酸無水物基を有するモノマーとしてNAH(無水ハイミックス酸、日立化成工業株式会社製)を、追加モノマーとしてCF2=CFO(CF2)3F(ペルフルオロプロピルビニルエーテル、旭硝子株式会社製)(以下、PPVEという)を用いて、接着性フルオロカーボン系樹脂(A)(接着性フッ素樹脂)を製造した。
接着性フルオロカーボン系樹脂(A)として、製造例で作製した射出成形可能なm-PFA、射出成形可能なフルオロカーボン系樹脂(B)として、旭硝子株式会社製PFA(製品名「Fluon(登録商標)PFA P-62XP」、比重(ρ)2.15)、熱可塑性ポリイミド(C)として、三井化学株式会社製TPI(製品名「AURUM(登録商標) PD-500」、比重(ρ)1.33)、添加剤(特定添加剤)として、炭素繊維(比重(ρ)1.7)、ガラス繊維(比重(ρ)2.5)、炭酸カルシウムウィスカ(比重(ρ)2.8)を用い、表1に示す容積基準の組成(表2には、質量基準の組成を示した)の樹脂組成物を、定法に従って、2軸混練押出機により調製し、ペレットを得た。得られた樹脂組成物を用い、定法に従って、射出成形により評価用サンプルとしてのシート状記録材剥離用摺動部材(射出成形品)を成形した。
実施例および比較例と同様に、表1(表2)に示す組成の樹脂組成物のペレットを得た。得られた樹脂組成物を用いて射出成形したシート状記録材剥離用摺動部材の表面に、定法に従って、PFAの融着被膜を形成したシート状記録材剥離用摺動部材を調製した。
実施例1~8、比較例1、2、参考例で調製した射出成形品(参考例については被膜形成後のもの。以下同じ。)を用いて、以下の項目について評価を行った。評価結果を表3に示す。
実施例などで調製した射出成形品の表面外観を目視により観察した。評価基準は、以下の通りである。
○:表面剥離なし
×:表面剥離あり
実施例および比較例で調製した射出成形品を用い、液体窒素に浸漬して冷凍した射出成形品を冷凍割断し、走査型電子顕微鏡(SEM)(日立ハイテクノロジーズ社製、S-3400N)にて観察して、TPIの粒子径を、SEM付属の測長機能を用いて測定した。
実施例などで調製した射出成形品を用い、JIS K7203に準拠して、25℃での曲げ試験を行った。
実施例などで調製した射出成形品を用い、JIS K7203に準拠して、200℃での曲げ試験を行った。
実施例などで調製した射出成形品を用い、表4の条件(但しステンレス鋼の温度は25℃)にてピンオンディスク式摩擦摩耗試験機により、ステンレス鋼に対する25℃での比摩耗量を測定した。尚、ステンレス鋼は、材質間の摩擦摩耗特性差を確認するための一般的な相手材であるため採用した。
実施例などで調製した射出成形品を用い、表4の条件(但しステンレス鋼の温度は200℃)にてピンオンディスク式摩擦摩耗試験機により、ステンレス鋼に対する200℃での比摩耗量を測定した。
実施例などで調製した射出成形品を用い、表4の条件(但しステンレス鋼の温度は25℃)にてピンオンディスク式摩擦摩耗試験機により、射出成形品のステンレス鋼に対する攻撃性を評価した。評価基準は、以下のとおりである。
○:ステンレス鋼の損傷深さ2μm以下
△:ステンレス鋼の損傷深さ2μmより大きく、10μm以下
実施例などで調製した射出成形品を用い、表4の条件(但しPFAの温度は200℃)にてピンオンディスク式摩擦摩耗試験機により、PFAに対する200℃での比摩耗量を測定した。尚、ロールの表面は、PFAで被覆されているのが一般的であるため、採用した。
実施例などで調製した射出成形品を用い、表4の条件(但しPFAの温度は200℃)にてピンオンディスク式摩擦摩耗試験機により、PFAに対する200℃での摩耗係数を測定した。
実施例などで調製した射出成形品を用い、表4の条件(但しPFAの温度は25℃)にてピンオンディスク式摩擦摩耗試験機により、射出成形品のPFAに対する攻撃性を評価した。評価基準は、以下のとおりである。
○:PFAの損傷深さが30μm以下
△:PFAの損傷深さが30μmより大きく、100μm以下
実施例などで調製した射出成形品を用い、自動接触角計(協和界面化学株式会社製、FACE自動接触角計CA-Z型)により、表面の水滴接触角を測定した。
実施例などで調製した射出成形品を用い、200℃のステンレス鋼ディスク上に、厚み2.5mm、先端角度45°、先端R0.05mmのエッジ部に1.96Nの荷重を与え、試験前と2時間後における荷重方向の寸法を測定し、試験前後の寸法差(変形量)を算出することにより、熱時変形特性を評価した。評価基準は、以下のとおりである。
◎:変形量が0.05mm未満
○:変形量が0.05mm以上、0.15mm未満
△:変形量が0.15mm以上
実施例1~8、比較例1、2、参考例について、材料コストについて評価した。評価基準は、以下のとおりである。
◎:PFAの射出成形材のkg単価
○:PFAの射出成形材のkg単価の4倍未満
実施例、比較例、参考例について、工程の容易さについて評価した。評価基準は、以下のとおりである。
○:被覆工程なし
△:被覆工程あり
上記の評価項目のうち、材料コストおよび工程の容易さにおいて、各評価基準の◎を2点、○を1点、△を0点と評点化し、両者の評点の和が、3~4点のものを◎、2点のものを○、0~1点のものを△として、製品コストを評価した。
上記の製造例において調製したm-PFAを用い、自動車用シールリング、ならびに、産業ガス圧縮機用シールリングまたは摺動部材としての適正を評価するための評価用サンプルを作製し、それらの評価を行った。そこで、先ず、各評価系について説明し、次に、各評価系に用いた各評価用サンプルの調製について説明する。
後述する実施例9~16および比較例3~9において作製した各評価用サンプルを用いて、平均分散粒子径測定および物性測定(曲げ試験)を行った。評価結果は、表7および表10に示す。
各分散粒子径測定用サンプルを、液体窒素に浸漬して冷凍したサンプルを冷凍割断し、断面をSEM(日立ハイテクノロジーズ社製、S-3400N)にて観察して、ドメインの粒子径を、SEM付属の測長機能を用いて測定した。平均分散粒子径は樹脂組成物に含まれる各成分の相容性を判断する指針となるものである。平均分散粒子径が、m-PFAを含まない場合に比べて小さくなっており、さらにそのサイズが小さくなっているほど、相容性が良好と判断することができる。
各物性測定用の評価サンプルを用いて、JIS K7203に準拠して曲げ試験を行い、曲げ弾性率、曲げ最大強度、曲げ破断歪を測定した。
上記の評価のうち、曲げ試験の結果をもとに、自動車用シールリング又は産業ガス圧縮機用シールリングもしくは摺動部材としての適合性を評価した。評価基準は、以下のとおりである。尚、高い機械強度の指標である曲げ強度としては、曲げ最大強度を採用した。
下記(i)および、(ii)または(iii)を満たすものを○とし、(i)および、(ii)または(iii)のいずれかを満たさないものを×とした。
(i)曲げ最大強度が30MPa以上である。
(ii)曲げ弾性率が1000MPa以上、2000MPa未満、かつ、曲げ破断歪が4%以上である。
(iii)曲げ弾性率が2000MPa以上、4000MPa未満、かつ、曲げ破断歪が2%以上である。
接着性フルオロカーボン系樹脂(A)として、製造例で作製したm-PFA、フルオロカーボン系樹脂(B)として、旭硝子株式会社製PFA(製品名「Fluon(登録商標)PFA P63」、比重2.15)、熱可塑性ポリイミド(C)として、三井化学株式会社製TPI(製品名「AURUM(登録商標) PD-500」、比重1.33)、を用い、表5に示す容積基準の組成(表6には、質量基準の組成を示した)の樹脂組成物を、定法に従って、2軸混練押出機(テクノベル社製、KZW15TW-45MG-NH)により調製し、ペレットとして得た。得られた樹脂組成物を用い、定法に従って圧縮成形により、前記の平均分散粒子径測定用の評価用サンプル(厚さ1mmシート)を成形した。また、定法に従ってトランスファー成形により、前記の物性測定用の評価サンプル(外径φ60mm×内径φ30mm×長さ100mmの略円筒形)を成形した。
表5に示す容積基準の組成(表6には、質量基準の組成を示した)の樹脂組成物を、実施例5と同様にして調製し、定法に従って圧縮成形により、物性測定用評価サンプル(外径φ60mm×内径φ30mm×長さ100mmの略円筒形)を成形した。
前記の三井化学株式会社製TPIを用いて、定法に従ってホットモールディング法にて圧縮成形して、後述する物性測定用評価サンプル(外径φ60mm×内径φ30mm×長さ100mmの略円筒形)を成形した。
PTFEとして、旭硝子株式会社製PTFE(製品名「Fluon(登録商標)PTFE G165」、比重2.17)を使用して、定法に従ってフリーベーキング法にて圧縮成形して、後述する物性測定用評価サンプル(外径φ60mm×内径φ30mm×長さ100mmの略円筒形)を成形した。
表8に示す容積基準の組成(表9には、質量基準の組成を示した)となるように各成分の粉末を、定法に従って、ミキサーにより撹拌混合した。得られた混合物をホットモールディング法にて圧縮成形して、表8(表9)に示す組成の樹脂組成物からなる物性測定用評価サンプル(外径φ60mm×内径φ30mm×長さ100mmの略円筒形)を成形した。なお、炭素繊維(CF)は、PAN系のミドル繊維(比重1.76)を使用した。
表8に示す容積基準の組成(表9には、質量基準の組成を示した)となるように各成分の粉末を、定法に従って、ミキサーにより撹拌混合した。得られた混合物をフリーベーキング法にて圧縮成形して、表8(表9)に示す組成の樹脂組成物からなる物性測定用評価サンプル(外径φ50mm×長さ50mmの略円柱)を成形した。
2 支軸
2a 軸孔
3 付勢手段
4 取付軸
10 ロール
11 回転軸
P 複写紙
θ 先端角度
Claims (10)
- 第1成分として、
接着性フルオロカーボン系樹脂(A)、または、
前記樹脂(A)と前記樹脂(A)とは異なるフルオロカーボン系樹脂(B)との容積比
(A/B)が5/95~99/1である樹脂混合物を、
第2成分として、熱可塑性ポリイミド(C)0.5~99容積%を含む樹脂組成物からなる、シート状記録材剥離用摺動部材、自動車用シールリング、又は、産業ガス圧縮機用シールリング若しくは摺動部材。 - 前記樹脂組成物が、添加剤を50容積%以下含む請求項1記載の、シート状記録材剥離用摺動部材、自動車用シールリング、又は、産業ガス圧縮機用シールリング若しくは摺動部材。
- 前記樹脂組成物において、前記樹脂(A)または前記樹脂混合物、前記熱可塑性ポリイミド(C)および前記添加剤の各容積比率の合計が100容積%である請求項2記載の、シート状記録材剥離用摺動部材、自動車用シールリング、又は、産業ガス圧縮機用シールリング若しくは摺動部材。
- 前記接着性フルオロカーボン系樹脂(A)が、酸無水物基、カルボキシ基、酸ハライド基およびカーボネート基からなる群より選択される少なくとも一種の官能基を有する請求項1~3のいずれか1項に記載の、シート状記録材剥離用摺動部材、自動車用シールリング、又は、産業ガス圧縮機用シールリング若しくは摺動部材。
- 前記接着性フルオロカーボン系樹脂(A)が、テトラフルオロエチレンに基づく第一繰返し単位、ジカルボン酸無水物基を有し、且つ環内に重合性不飽和基を有する環状炭化水素モノマーに基づく第二繰返し単位、および、その他のモノマーに基づく第三繰返し単位を含有し、第一繰返し単位、第二繰返し単位および第三繰返し単位の合計モル量に対して、第一繰返し単位が50~99.89モル%、第二繰返し単位が0.01~5モル%、第三繰返し単位が0.1~49.99モル%である含フッ素共重合体である請求項1~4のいずれか1項に記載の、シート状記録材剥離用摺動部材、自動車用シールリング、又は、産業ガス圧縮機用シールリング若しくは摺動部材。
- 前記接着性フルオロカーボン系樹脂(A)および前記フルオロカーボン系樹脂(B)が射出成形可能な樹脂であり、
前記熱可塑性ポリイミド(C)の含有量が0.5~50容積%である、請求項1~5のいずれか1項に記載のシート状記録材剥離用摺動部材。 - 前記樹脂組成物が、前記添加剤として繊維状物質、ウィスカ状物質、および粒子状物質からなる群より選択される少なくとも1種を0.1~30容積%含む請求項6記載のシート状記録材剥離用摺動部材。
- 前記熱可塑性ポリイミド(C)の平均分散粒子径が10μm以下である請求項6または7記載のシート状記録材剥離用摺動部材。
- 表面の水滴接触角が90°以上である請求項6~8のいずれか1項に記載のシート状記録材剥離用摺動部材。
- 前記熱可塑性ポリイミド(C)を1~99容積%含む請求項1~5のいずれか1項に記載の自動車用シールリング、又は、産業ガス圧縮機用シールリング若しくは摺動部材。
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PCT/JP2011/075997 WO2012070401A1 (ja) | 2010-11-24 | 2011-11-10 | シート状記録材剥離用摺動部材、自動車用シールリング、並びに、産業ガス圧縮機用シールリング及び摺動部材 |
Country Status (6)
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US (1) | US9388009B2 (ja) |
EP (1) | EP2645178B1 (ja) |
KR (1) | KR101908289B1 (ja) |
CN (2) | CN104945795B (ja) |
HK (1) | HK1212721A1 (ja) |
WO (1) | WO2012070401A1 (ja) |
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JP2020526654A (ja) * | 2017-07-14 | 2020-08-31 | アーケマ・インコーポレイテッド | 高強度ポリフッ化ビニリデン複合体 |
WO2022220007A1 (ja) * | 2021-04-15 | 2022-10-20 | 三菱瓦斯化学株式会社 | 熱可塑性ポリイミド樹脂組成物及び成形品 |
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KR20180004710A (ko) | 2015-05-11 | 2018-01-12 | 아사히 가라스 가부시키가이샤 | 프린트 기판용 재료, 금속 적층판, 그들의 제조 방법 및 프린트 기판의 제조 방법 |
US10844153B2 (en) | 2015-05-11 | 2020-11-24 | AGC Inc. | Material for printed circuit board, metal laminate, methods for producing them, and method for producing printed circuit board |
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WO2022220007A1 (ja) * | 2021-04-15 | 2022-10-20 | 三菱瓦斯化学株式会社 | 熱可塑性ポリイミド樹脂組成物及び成形品 |
Also Published As
Publication number | Publication date |
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US20130313774A1 (en) | 2013-11-28 |
EP2645178A4 (en) | 2018-07-04 |
US9388009B2 (en) | 2016-07-12 |
KR101908289B1 (ko) | 2018-10-16 |
HK1212721A1 (zh) | 2016-06-17 |
CN103314332A (zh) | 2013-09-18 |
CN103314332B (zh) | 2017-02-15 |
CN104945795B (zh) | 2019-05-21 |
KR20130107333A (ko) | 2013-10-01 |
EP2645178B1 (en) | 2021-06-23 |
CN104945795A (zh) | 2015-09-30 |
EP2645178A1 (en) | 2013-10-02 |
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