WO2013088964A1 - 樹脂組成物及び成形品 - Google Patents
樹脂組成物及び成形品 Download PDFInfo
- Publication number
- WO2013088964A1 WO2013088964A1 PCT/JP2012/080913 JP2012080913W WO2013088964A1 WO 2013088964 A1 WO2013088964 A1 WO 2013088964A1 JP 2012080913 W JP2012080913 W JP 2012080913W WO 2013088964 A1 WO2013088964 A1 WO 2013088964A1
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- WIPO (PCT)
- Prior art keywords
- fluororesin
- resin
- resin composition
- particle size
- polyether ketone
- Prior art date
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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
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2650/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
- C08G2650/28—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type
- C08G2650/38—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group
- C08G2650/40—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule characterised by the polymer type containing oxygen in addition to the ether group containing ketone groups, e.g. polyarylethylketones, PEEK or PEK
Definitions
- the present invention relates to a resin composition and a molded article.
- thermoplastic resins such as polyamide resins, polycarbonate resins, polyacetal resins, etc.
- Electrical and electronic parts have been put into practical use.
- sliding applications such as gears and bearing retainers, the replacement of metal sliding members with plastic sliding members is progressing, but the sliding members are used under conditions such as high load, high temperature, and high speed rotation.
- the above-mentioned thermoplastic resin has insufficient slidability, and problems such as wear, melting, cracking and chipping may occur.
- fluororesins are excellent in properties such as slidability, heat resistance, chemical resistance, solvent resistance, weather resistance, flexibility, electrical properties, etc., and are widely used in automobiles, industrial machines, OA equipment, electrical and electronic equipment, etc. Used in the field.
- the fluororesin is particularly excellent in slidability, and its low coefficient of friction is prominent among the resins.
- it is often inferior to physical heat resistance as indicated by mechanical properties and deflection temperature under load compared to crystalline heat-resistant thermoplastic resin, and dimensions compared to amorphous heat-resistant thermoplastic resin. In some cases, the stability is inferior, and the range of use is limited.
- Patent Document 1 discloses that a total amount of fluororesin and graphite is 1 with respect to 100 parts by weight of a resin composition comprising 60 to 99 parts by weight of a thermoplastic resin having a heat deformation temperature of 100 ° C. or higher and 40 to 1 part by weight of carbon fibers.
- a resin composition containing ⁇ 50 parts by weight is disclosed.
- Patent Document 2 includes a thermoplastic heat-resistant resin (A) having a molding temperature of 300 ° C. or higher and a polymer (B) obtained by polymerizing ⁇ -fluoroacrylic acid fluoroacrylic having a specific structure as essential components.
- Patent Document 3 includes (A) 70 to 99% by mass of a polyaryl ketone resin and (B) 30 to 1% by mass of a fluororesin, and the average particle size of (B) the fluororesin dispersed in the resin composition is A resin composition having a thickness of 0.1 to 30 ⁇ m has been proposed.
- Patent Document 4 discloses a resin composition comprising a resin other than a fluororesin (component (A)) and a fluororesin (component (B)), and a resin other than a sea phase fluororesin (component ( A)) having a sea-island structure in which the island-phase fluororesin (component (B)) is dispersed, and the average particle diameter of the island-phase fluororesin (component (B)) is 200 ⁇ m or less.
- a resin composition is proposed.
- Patent Document 5 discloses a melt flow index of 400 ° C.
- Patent Document 6 proposes a modified engineering plastic characterized by cross-linking a mixture of engineering plastic and fluorine resin.
- Patent Document 7 discloses that at least a part of carbon atoms constituting the fluororesin molecular chain has a crosslinked structure with other carbon atoms constituting the molecular chain, and at least a part of the fluororesin molecule is an active terminal.
- a thermoplastic resin composition comprising at least 5 to 40 parts by mass of a fluororesin having a group and 95 to 60 parts by mass of another thermoplastic resin.
- Patent Document 8 In addition to the purpose of improving the slidability, it is known to add a fluororesin to the thermoplastic resin.
- Patent Document 8 in order to improve molding processability such as reducing extrusion pressure and extrusion torque in engineering plastic molding, the mass of the engineering plastic and the mass of the fluoropolymer are added. It is disclosed that 0.005 to 1% by mass of the total of the above is added.
- Patent Document 9 a fine powder of PEEK resin is mixed in a PFA: PEEK weight ratio of 75:25 to 70:30 in a PFA resin aqueous dispersion, and the dispersion is roughened according to a conventional method.
- Patent Document 10 discloses a thermoplastic resin containing a mixture of a polyaryl ketone resin and a thermoplastic fluororesin, wherein the continuous phase of the mixture is the thermoplastic fluororesin, and the dispersed phase is a polyaryl ketone resin. A composition is described.
- Patent Document 11 aims to provide a film having a high Young's modulus, a low dielectric constant, excellent flame retardancy, heat resistance, insulation, and high rigidity, and an FPC using the film as a base material.
- a polyaryl ketone film characterized by being stretched in the direction has been proposed.
- Polyetheretherketone resin exhibits relatively excellent sliding properties among thermoplastic resins and has been put to practical use in sliding applications such as gears and bearing retainers. However, the slidability is still not sufficient under severe sliding conditions such as high loads, and a PEEK composition containing PTFE powder has been developed and marketed in order to improve the slidability of PEEK. Although the PTFE powder-blended PEEK composition has a reduced coefficient of dynamic friction, the sliding characteristics represented by the limit PV value are at a low level, and further improvement in sliding performance is required.
- JP-A-8-48887 JP-A-10-195302 JP 2006-274073 A Japanese Patent Laid-Open No. 2002-235011 JP-A-9-87517 JP 2002-146202 A JP 2004-137363 A International Publication No. 2003/044093 Pamphlet JP-A-6-316686 JP 2010-189599 A JP 2003-82123 A
- an object of this invention is to provide the resin composition which can obtain the molded article which has a low dynamic friction coefficient and a high limit PV value.
- the present inventors diligently studied about a resin composition capable of obtaining a molded product having a low dynamic friction coefficient and a high limit PV value, and focused on a resin composition containing an aromatic polyetherketone resin and a fluororesin. .
- the specific fluororesin is dispersed in the aromatic polyetherketone resin with a specific average dispersed particle size, and the melt viscosity ratio of the aromatic polyetherketone resin and the fluororesin is in a specific range.
- Rf 2 represents a perfluoroalkyl group having 1 to 5 carbon atoms
- the mass ratio (I) :( II) of the aromatic polyether ketone resin (I) to the fluororesin (II) is 95: 5 to 50:50
- the aromatic polyether ketone resin (I) Viscosity ratio (I) / (II) of styrene and fluororesin (II) is 0.3 to 5.0
- fluororesin (II) is dispersed in the form of particles in aromatic polyetherketone resin (I)
- the resin composition is characterized in that the average dispersed particle size of the fluororesin (II) is less than 3.0 ⁇ m.
- the fluororesin (II) is dispersed in the form of particles in the aromatic polyetherketone resin (I), and the average dispersed particle size of the fluororesin (II) is less than 0.3 ⁇ m.
- the maximum dispersed particle size is preferably 0.8 ⁇ m or less.
- the fluororesin (II) preferably has a melt flow rate of 0.1 to 100 g / 10 min.
- the aromatic polyether ketone resin (I) is preferably a polyether ether ketone.
- the present invention is also a molded article made of the above resin composition.
- the molded product of the present invention is preferably used as a sliding member.
- the molded article of the present invention is preferably a sealing material, gear, actuator, piston, bearing or bush.
- the resin composition of this invention consists of the said structure, the molded article which has a low dynamic friction coefficient and a high limit PV characteristic can be obtained. Thereby, the obtained molded article shows excellent slidability.
- the resin composition of the present invention contains an aromatic polyether ketone resin (I) and a fluororesin (II).
- the aromatic polyether ketone resin (I) is preferably at least one resin selected from the group consisting of polyether ketone, polyether ether ketone, polyether ketone ketone and polyether ketone ether ketone ketone. More preferred is at least one resin selected from the group consisting of polyetherketone and polyetheretherketone, and even more preferred is polyetheretherketone.
- the aromatic polyether ketone resin (I) preferably has a melt viscosity of 0.25 to 1.50 kNsm ⁇ 2 at 60 sec ⁇ 1 and 390 ° C.
- the melt viscosity is in the above range, the processing characteristics are improved, and a molded product having a low dynamic friction coefficient and a high limit PV characteristic is obtained.
- a preferred lower limit for the melt viscosity is 0.80 kNsm -2 .
- a preferred upper limit for the melt viscosity is 1.30 kNsm -2 .
- the melt viscosity of the aromatic polyether ketone resin (I) is measured according to ASTM D3835.
- the aromatic polyether ketone resin (I) preferably has a glass transition temperature of 130 ° C. or higher. More preferably, it is 135 degreeC or more, More preferably, it is 140 degreeC or more. When the glass transition temperature is in the above range, a resin composition having excellent heat resistance can be obtained. The glass transition temperature is measured by a differential scanning calorimetry (DSC) apparatus.
- DSC differential scanning calorimetry
- the aromatic polyether ketone resin (I) preferably has a melting point of 300 ° C. or higher. More preferably, it is 320 degreeC or more. When the melting point is in the above range, the heat resistance of the obtained molded product can be improved. The melting point is measured by a differential scanning calorimetry (DSC) apparatus.
- DSC differential scanning calorimetry
- fluororesin (II) 1 type may be used and 2 or more types may be used.
- Rf 1 is —ORf 2
- Rf 2 is preferably a perfluoroalkyl group having 1 to 3 carbon atoms.
- a molded product having a lower coefficient of dynamic friction and a higher limit PV value can be obtained, so hexafluoropropylene, perfluoro (methyl vinyl ether) , Preferably at least one selected from the group consisting of perfluoro (ethyl vinyl ether) and perfluoro (propyl vinyl ether), and at least one selected from the group consisting of hexafluoropropylene and perfluoro (propyl vinyl ether) It is more preferable that
- fluororesin (II) a perfluoropolymer is preferable because a low dynamic friction coefficient can be obtained.
- the fluororesin (II) is preferably composed of 80 to 99 mol% of TFE and 1 to 20 mol% of a perfluoroethylenically unsaturated compound represented by the general formula (1).
- the lower limit of the content of TFE constituting the fluororesin (II) is more preferably 85 mol%, further preferably 87 mol%, particularly preferably 90 mol%, and particularly preferably 93 mol%.
- the upper limit of the content of TFE constituting the fluororesin (II) is more preferably 97 mol%, still more preferably 95 mol%.
- the lower limit of the content of the perfluoroethylenically unsaturated compound represented by the general formula (1) constituting the fluororesin (II) is more preferably 3 mol%, further preferably 5 mol%.
- the upper limit of the content of the perfluoroethylenically unsaturated compound represented by the general formula (1) constituting the fluororesin (II) is more preferably 15 mol%, further preferably 13 mol%, and more preferably 10 mol%. Is particularly preferred, with 7 mol% being even more preferred.
- the fluororesin (II) preferably has a melt viscosity of 0.3 to 3.0 kNsm -2 at 60 sec -1 and 390 ° C.
- the melt viscosity is in the above range, the processing characteristics are improved, and a low dynamic friction coefficient and a high limit PV characteristic can be obtained.
- a more preferable lower limit of the melt viscosity is 0.4 kNsm ⁇ 2 .
- the upper limit of the melt viscosity is more preferably 2.5 kNsm -2 , further preferably 2.0 kNsm -2 .
- the melt viscosity of the fluororesin (II) is measured according to ASTM D3835.
- the fluororesin (II) preferably has a melt flow rate (MFR) measured at 372 ° C. under a load of 5000 g of 0.1 to 100 g / 10 min, preferably 5 to 40 g / 10 min. More preferably, it is 10 to 40 g / 10 min.
- MFR melt flow rate
- the more preferable lower limit of MFR is 12 g / 10 minutes, and the particularly preferable lower limit is 15 g / 10 minutes.
- the more preferable upper limit of MFR is 38 g / 10 minutes, and the particularly preferable upper limit is 35 g / 10 minutes.
- the MFR of the fluororesin (II) is measured using a melt indexer according to ASTM D3307-01.
- the melting point of the fluororesin (II) is not particularly limited, but it is preferable in molding that the fluororesin (II) is already melted at a temperature at which the aromatic polyetherketone resin (I) used in molding is melted.
- the temperature is preferably not higher than the melting point of the aromatic polyether ketone resin (I).
- the melting point of the fluororesin (II) is preferably 230 to 350 ° C.
- the melting point of the fluororesin (II) is determined as a temperature corresponding to the maximum value in the heat of fusion curve when the temperature is raised at a rate of 10 ° C./min using a differential scanning calorimetry (DSC) apparatus.
- DSC differential scanning calorimetry
- the fluororesin (II) may be treated with fluorine gas by a known method or may be treated with ammonia.
- the resin composition of the present invention comprises a melt viscosity ratio (I) / (II) (aromatic polyetherketone resin (I) / fluororesin (II) of aromatic polyetherketone resin (I) and fluororesin (II). )) Is 0.3 to 5.0.
- a melt viscosity ratio (I) / (II) is more preferably 0.4 to 4.0, and still more preferably 0.5 to 3.0.
- (II) is particularly preferably 0.5 to 2.5.
- the mass ratio (I) :( II) of the aromatic polyether ketone resin (I) to the fluororesin (II) is 95: 5 to 50:50.
- the mass ratio (I) :( II) is in the above range, a molded product having both a low dynamic friction coefficient and a high limit PV characteristic can be produced. If the content of the fluororesin (II) exceeds 50 by mass ratio with the aromatic polyetherketone resin (I), the strength tends to be inferior, and if it is less than 5, a sufficient dynamic friction coefficient cannot be obtained.
- a more preferred range is 90:10 to 60:40.
- the fluororesin (II) is dispersed in the form of particles in the aromatic polyetherketone resin (I), and the average dispersed particle size of the fluororesin (II) is less than 3.0 ⁇ m. .
- the average dispersed particle size is less than 3.0 ⁇ m, a molded product having both a low dynamic friction coefficient and a high critical PV characteristic can be produced. If the average dispersed particle size is too large, sufficient slidability cannot be obtained.
- an aromatic polyether ketone having improved impact resistance has been demanded in order to eliminate cracking and chipping of the sliding member.
- a method of alloying a rubber component is employed.
- the aromatic polyether ketone is a high heat-resistant thermoplastic resin, and the molding process temperature exceeds 350 ° C., and the molding is usually performed near 400 ° C. Even if the rubber component is alloyed with the aromatic polyether ketone, the rubber component is thermally deteriorated at the time of molding and is not practical. Therefore, the present condition is that the effective means for improving the impact resistance of aromatic polyether ketone has not been found substantially.
- the present inventors have dispersed the fluororesin (II) in the form of particles in the aromatic polyetherketone resin (I), and the average dispersed particle size of the fluororesin (II) is It has been found that by using a resin composition having a size of less than 3.0 ⁇ m, not only a molded product having a low dynamic friction coefficient and a high limit PV characteristic is obtained, but also the impact resistance of the molded product is dramatically improved. It was.
- the average dispersed particle size of the fluororesin (II) is preferably 2.0 ⁇ m or less, More preferably, it is 0.3 ⁇ m or less.
- the lower limit of the average dispersed particle size is not particularly limited, but may be 0.01 ⁇ m.
- the average dispersed particle size of the fluororesin (II) is less than 0.3 ⁇ m and the maximum dispersed particle size is 0.8 ⁇ m or less.
- the average dispersed particle size is less than 0.3 ⁇ m and the maximum dispersed particle size is 0.8 ⁇ m or less, the slidability of the dynamic friction coefficient and the limit PV value is improved, and a thin film with less fish eyes can be produced. It becomes possible. Moreover, the impact resistance of the molded article obtained from the resin composition of the present invention is dramatically improved.
- the maximum dispersed particle size of the fluororesin (II) is preferably 0.75 ⁇ m or less, preferably 0.70 ⁇ m or less. More preferably.
- the average dispersed particle size and the maximum dispersed particle size of the fluororesin (II) can be measured by observing the resin composition of the present invention with a confocal laser microscope or by using a press sheet prepared from the resin composition of the present invention. It can be determined by cutting out a thin slice, performing microscopic observation of the ultrathin slice with a transmission electron microscope (TEM), and binarizing the obtained image with an optical analyzer.
- TEM transmission electron microscope
- the resin composition of the present invention contains an aromatic polyether ketone resin (I) and a fluororesin (II), but may contain other components as necessary.
- Fibrous reinforcement materials such as whisker, such as potassium titanate, glass fiber, asbestos fiber, carbon fiber, ceramic fiber, potassium titanate fiber, aramid fiber, and other high-strength fibers
- Inorganic fillers such as calcium carbonate, talc, mica, clay, carbon powder, graphite and glass beads; colorants; inorganic or organic fillers usually used such as flame retardants; stabilizers such as minerals and flakes; silicone oil Lubricants such as molybdenum disulfide; pigments; conductive agents such as carbon black; impact resistance improvers such as rubber; and other additives.
- the resin composition of the present invention is obtained by mixing the aromatic polyetherketone resin (I) and the fluororesin (II) with a twin screw extruder having a screw configuration with an L / D of 35 or more. It is preferable to be obtained.
- Examples of the method for producing the resin composition of the present invention include a method in which the aromatic polyether ketone resin (I) and the fluororesin (II) are mixed in a molten state.
- the resin composition of the present invention having a desired dispersion state can be obtained. Since the dispersion state affects the dynamic friction coefficient and the limit PV characteristics of the molded product, as well as the formation and moldability of the thin film, the kneading method can be used to obtain the desired dispersion state in the molded product obtained from the resin composition. Selection should be made appropriately.
- the aromatic polyetherketone resin (I) and the fluororesin (II) are introduced into a mixer at an appropriate ratio, and the above-mentioned other components are added as desired. And a method of producing by melting and kneading the resin (I) and (II) above the melting point.
- the other components may be added to the aromatic polyether ketone resin (I) and the fluororesin (II) in advance and mixed, or the aromatic polyether ketone resin (I) and the fluororesin (II). You may add when mix
- the temperature at the time of the melt kneading may be appropriately set depending on the kind of the aromatic polyetherketone resin (I) and the fluororesin (II) to be used, but it is preferably, for example, 360 to 400 ° C.
- the kneading time is usually 1 minute to 1 hour.
- the said resin composition can make the dynamic friction coefficient of the molded object obtained from this resin composition 0.22 or less.
- the coefficient of dynamic friction is in the above range, it can be more suitably used as a molded article for a sliding member.
- the dynamic friction coefficient is more preferably 0.21 or less.
- the said resin composition can make the limit PV value of the molded object obtained from this resin composition into 800 or more. More preferably, it is 1000 or more, More preferably, it is 1300 or more, Especially preferably, it is 1500 or more.
- the resin composition can have a notched Izod strength of a molded product obtained from the resin composition of 30 kJ / m 2 or more. More preferably, it is 40 kJ / m 2 or more. In order to obtain high Izod strength, it is necessary to control the average dispersed particle size of the fluororesin (II) to less than 0.3 ⁇ m. Further, from the viewpoint of preventing cracking and chipping of the molded product, it is also preferable that the obtained molded product has a notched Izod strength of 60 kJ / m 2 or more.
- a molded article formed from the resin composition of the present invention is also one aspect of the present invention.
- Molded articles formed from the resin composition of the present invention have slidability and impact resistance, as well as heat resistance, chemical resistance, solvent resistance, strength, rigidity, low chemical permeability, dimensional stability, and flame resistance.
- the electrical / electronics / semiconductor field it is a semiconductor retainer / liquid crystal manufacturing equipment component such as CMP retainer ring, etching ring, silicon wafer carrier, IC chip tray, insulation film, and small button battery.
- Cable connectors aluminum electrolytic capacitor body cases; in the automotive field, thrust washers, oil filters, auto air conditioner control unit gears, throttle body gears, ABS parts, AT seal rings, MT shift fork pads, bearings, seals, clutches Ring; In the industrial field, compressor parts, Mass transit system cables, conveyor belt chains, connectors for oilfield development machinery, hydraulic drive system pump parts (bearings, port plates, piston ball joints); in the aerospace field, aircraft cabin interior parts, fuel pipe protection materials ; And food / beverage production equipment parts, medical equipment parts (sterilization equipment, gas / liquid chromatograph), and the like.
- the said molded article does not specifically limit as a shape of the said molded article,
- it can be set as various shapes, such as a sheet form; a film form; a rod form;
- the molded article of the present invention is particularly suitable for a sheet-like or film-like molded article because it can produce a thin film with little fish eye.
- This invention is also a molded article for sliding members which consists of the said resin composition. Since the molded product for sliding members molded using the resin composition has a low coefficient of dynamic friction, it can be suitably used as a sliding member. Moreover, since it contains a fluororesin, it is excellent in chemical resistance, weather resistance, non-adhesiveness, water repellency, electrical properties and the like. Although it does not specifically limit as said molded article for sliding members, For example, a sealing material, a gear, an actuator, a piston, a bearing, a bearing retainer, a bush, a switch, a belt, a bearing, a cam, a roller, a socket etc. are mentioned.
- the molding temperature is preferably a temperature equal to or higher than the melting point of the aromatic polyether ketone resin (I) used.
- the molding temperature is preferably a temperature lower than the lower one of the decomposition temperature of the fluororesin (II) and the decomposition temperature of the aromatic polyether ketone resin (I).
- Such a molding temperature may be 250 to 400 ° C., for example.
- the molded product of the present invention is generally a thermoplastic resin composition such as injection molding, extrusion molding, press molding, blow molding, calendar molding, casting molding, etc., depending on the type, application, shape, etc. of the target molded product. It can shape
- the dynamic friction coefficient was calculated
- the number of fish eyes was determined by measuring the number of fish eyes of a 12 cm ⁇ 50 cm square film having a thickness of 25 ⁇ m produced by the T-die extrusion method. ⁇ : Less than 10 ⁇ : 10 or more and less than 30 ⁇ : 30 or more
- melt viscosity of the aromatic polyetherketone resin was measured at 60 sec ⁇ 1 and 390 ° C. according to ASTM D3835.
- the melt viscosity of the fluororesin was measured at 60 sec ⁇ 1 and 390 ° C. in accordance with ASTM D3835.
- Aromatic polyether ketone resin (1) Polyether ether ketone (melt viscosity; 1.48 kNsm ⁇ 2 )
- Aromatic polyetherketone resin (2) polyetheretherketone (melt viscosity; 1.19 kNsm ⁇ 2 )
- Aromatic polyetherketone resin (3) polyetheretherketone (melt viscosity; 0.31 kNsm ⁇ 2 )
- Fluororesin (4) Polytetrafluoroethylene (trade name: Lubron L5, manufactured by Daikin Industries, Ltd.)
- Fluororesin (5) ethylene / tetrafluoroethylene copolymer (trade name: NEOFLON EP541, manufactured by Daikin Industries, Ltd., melt viscosity; 2.27 kNsm ⁇ 2 )
- a resin composition was produced by melt-kneading under conditions of a temperature of 390 ° C. and a screw rotation speed of 300 rpm.
- a test piece was prepared by the above-described method, and the limit PV value, dynamic friction coefficient, and notched Izod strength were measured. Further, the average dispersed particle size and the maximum dispersed particle size of the fluororesin (II) were calculated with the test piece.
- the resin composition was manufactured by melt-kneading under conditions of a temperature of 390 ° C. and a screw rotation speed of 500 rpm.
- a test piece was prepared by the above-described method, and the limit PV value, dynamic friction coefficient, and notched Izod strength were measured. Further, the average dispersed particle size and the maximum dispersed particle size of the fluororesin (1) were calculated with the test piece.
- a resin composition was produced by melt-kneading under conditions of a temperature of 390 ° C. and a screw rotation speed of 300 rpm.
- a test piece was prepared by the above-described method, and the limit PV value, dynamic friction coefficient, and notched Izod strength were measured. Further, the average dispersed particle size and the maximum dispersed particle size of the fluororesin (1) were calculated with the test piece.
- the resin composition was manufactured by melt-kneading under conditions of a temperature of 390 ° C. and a screw rotation speed of 500 rpm.
- a test piece was prepared by the above-described method, and the limit PV value, dynamic friction coefficient, and notched Izod strength were measured. Further, the average dispersed particle size and the maximum dispersed particle size of the fluororesin (3) were calculated with the test piece.
- the resin composition was manufactured by melt-kneading under conditions of a temperature of 390 ° C. and a screw rotation speed of 500 rpm.
- a test piece was prepared by the above-described method, and the limit PV value, dynamic friction coefficient, and notched Izod strength were measured. Further, the average dispersed particle size and the maximum dispersed particle size of the fluororesin (1) were calculated with the test piece.
- a press sheet was prepared by the above-described method, and a limit PV value, a dynamic friction coefficient, and a notched Izod strength were measured.
- the ultra-thin slice was cut out from the press sheet, and the average dispersed particle size and the maximum dispersed particle size of the fluororesin (4) or (5) were calculated.
- a resin composition was produced by melt-kneading under conditions of a temperature of 390 ° C. and a screw rotation speed of 300 rpm.
- a press sheet was prepared by the above-described method, and a limit PV value, a dynamic friction coefficient, and a notched Izod strength were measured.
- the ultra-thin slice was cut out from the press sheet, and the average dispersed particle size and the maximum dispersed particle size of the fluororesin (2) were calculated.
- a slit table having a width of 500 mm
- stretching with a take-up roll of 130 ° C. creating a film stretched to 25 ⁇ m
- average dispersed particles of fluororesin (1) The diameter and the maximum dispersed particle diameter were calculated.
- the resin composition of the present invention can be suitably used as a molding material used for automobile parts, industrial parts, electrical and electronic parts and the like that require high slidability.
Abstract
Description
CF2=CF-Rf1 (1)
(式中、Rf1は、-CF3又は-ORf2を表す。Rf2は、炭素数1~5のパーフルオロアルキル基を表す。)で表されるパーフルオロエチレン性不飽和化合物の共重合体であり、芳香族ポリエーテルケトン樹脂(I)とフッ素樹脂(II)との質量比(I):(II)が95:5~50:50であり、芳香族ポリエーテルケトン樹脂(I)とフッ素樹脂(II)との溶融粘度比(I)/(II)が0.3~5.0であり、フッ素樹脂(II)が芳香族ポリエーテルケトン樹脂(I)中に粒子状に分散しており、フッ素樹脂(II)の平均分散粒子径が3.0μm未満であることを特徴とする樹脂組成物である。
上記芳香族ポリエーテルケトン樹脂(I)の溶融粘度は、ASTM D3835に準拠して測定する。
CF2=CF-Rf1 (1)
(式中、Rf1は、-CF3又は-ORf2を表す。Rf2は、炭素数1~5のパーフルオロアルキル基を表す。)で表されるパーフルオロエチレン性不飽和化合物の共重合体である。フッ素樹脂(II)としては、1種を用いてもよいし、2種以上を用いてもよい。上記Rf1が、-ORf2である場合、上記Rf2は炭素数が1~3のパーフルオロアルキル基であることが好ましい。
上記フッ素樹脂(II)を用いることによって、低い動摩擦係数及び高い限界PV値を兼ね備えた成形品を得ることができる。例えば、非溶融加工性のポリテトラフルオロエチレンを用いた場合には、充分に低い磨耗特性を有する成形品を得ることができない。
また、上記フッ素樹脂(II)を構成する上記一般式(1)で表されるパーフルオロエチレン性不飽和化合物の含有量の下限は、3モル%がより好ましく、5モル%が更に好ましい。上記フッ素樹脂(II)を構成する上記一般式(1)で表されるパーフルオロエチレン性不飽和化合物の含有量の上限は、15モル%がより好ましく、13モル%が更に好ましく、10モル%が特に好ましく、7モル%が殊更に好ましい。
上記フッ素樹脂(II)の溶融粘度は、ASTM D3835に準拠して測定する。
上記フッ素樹脂(II)のMFRは、ASTM D3307-01に準拠し、メルトインデクサーを用いて測定する。
特に、フィッシュアイの少ない薄膜を得ることができる点、及び、ノッチ付きアイゾッド強度がより優れる点、平均分散粒子径及び最大分散粒子径を小さくすることができる点から、溶融粘度比(I)/(II)は0.5~2.5であることが特に好ましい。
このような現状のもと、本発明者らは、フッ素樹脂(II)が芳香族ポリエーテルケトン樹脂(I)中に粒子状に分散しており、フッ素樹脂(II)の平均分散粒子径が3.0μm未満である樹脂組成物を用いることによって、低動摩擦係数及び高い限界PV特性を有する成形品となるばかりか、意外なことに成形品の耐衝撃性が劇的に向上することを見出した。
平均分散粒子径の下限は特に限定されないが0.01μmであってよい。
平均分散粒子径が0.3μm未満であり、且つ最大分散粒子径が0.8μm以下であると、動摩擦係数や限界PV値の摺動性が向上するとともに、フィッシュアイの少ない薄膜フィルムの作成が可能となる。また、本発明の樹脂組成物から得られる成形品の耐衝撃性が劇的に向上する。
上記のことから、本発明の樹脂組成物は、芳香族ポリエーテルケトン樹脂(I)及びフッ素樹脂(II)を、L/Dが35以上であるスクリュウ構成の二軸押出機で混合することにより得られるものであることが好ましい。
芳香族ポリエーテルケトン樹脂(I)とフッ素樹脂(II)とを充分に混練することによって、所望の分散状態を有する本発明の樹脂組成物を得ることができる。分散状態は成形品の動摩擦係数及び限界PV特性、並びに、薄膜フィルムの作成、成形性に影響を与えるので、樹脂組成物から得られる成形品において所望の分散状態が得られるように、混練方法の選択は適切に行われるべきである。
また、成形品の割れや欠けを防止する観点からは、得られる成形体のノッチ付きアイゾット強度が60kJ/m2以上であることも好ましい。
上記成形品の形状としては特に限定されず、例えば、シート状;フィルム状;ロッド状;パイプ状等の種々の形状にすることができる。本発明の成形品は、フィッシュアイの少ない薄膜を作製することができるため、シート状、フィルム状の成形品に特に好適である。
上記摺動部材用成形品としては、特に限定されないが、例えば、シール材、ギア、アクチュエーター、ピストン、ベアリング、ベアリングリテーナ、ブッシュ、スイッチ、ベルト、軸受け、カム、ローラー、ソケット等が挙げられる。
ASTM D3307-01に従って、メルトインデクサー((株)東洋精機製作所製)を用いて、372℃、5000g荷重下で内径2mm、長さ8mmのノズルから10分間あたりに流出するポリマーの質量(g/10分)を求めた。
実施例、比較例で製造した樹脂組成物を用いて、熱プレス機により380℃、5MPaの条件下で圧縮成形し、厚さ3mmのシートを作製した。
上述した方法で作成したプレスシートから、縦3cm・横3cm・厚み3mmの試験片を切り出し、JIS K7218のA法に準じて、摩擦摩耗試験機(株式会社エー・アンド・デイ製)を使用して、鋼材S45C(#240サンドペーパー仕上げ)を相手材に、速度3m/秒一定、面圧を20Nから10分毎に20Nずつ上昇させることにより、限界PV値を測定した。
上述した方法で作製したプレスシートを用いて、ボールオンディスク型のSRV摩擦磨耗試験機(OPTIMOL社製)により、室温、50Hzの条件で、動摩擦係数を求めた。
上述した方法で作成したプレスシートから、JIS K7110に準じて、ノッチ付きアイゾッド強度測定用の試験片を切り出し、アイゾッド衝撃試験機((株)東洋精機製作所製)を使用して、室温にてノッチ付きアイゾッド強度を測定した。
フィッシュアイ個数の判定は、Tダイ押出の方法で作製した12cm×50cm四方、厚み25μmのフィルムのフィッシュアイ個数を計測した。
○:10個未満
△:10個以上30個未満
×:30個以上
上述した方法で作成したプレスシートを用いて、先端部分が1mm四方になるようトリミング用剃刀でトリミングを行い、その後、ウルトラミクロトーム(ライカ社製ULTRACUT S)の試料ホルダーに固定、チャンバー内を液体窒素で-80℃まで冷却し、厚さ90nmの超薄切片を切り出した。
得られた超薄切片を20%エタノール溶液を付着させた白金リングにて回収し、銅製シートメッシュ(応研商事(株)製200A、φ3.0mm)に付着させた。
その後、透過型電子顕微鏡((株)日立製作所製H7100FA)を用いて、銅製シートメッシュに付着させた超薄切片の観察を行った。
顕微鏡観察により得られたネガフィルムをスキャナー(EPSON(株)製GT-9400UF)にて電子画像化し、光学解析装置((株)ニレコ製LUZEX AP)を用いて電子像の二値化処理を行い、分散相の平均分散粒子径及び最大分散粒子径を求めた。
芳香族ポリエーテルケトン樹脂の溶融粘度は、60sec-1、390℃において、ASTM D3835に準拠して測定した。
フッ素樹脂の溶融粘度は、60sec-1、390℃において、ASTM D3835に準拠して測定した。
芳香族ポリエーテルケトン樹脂(1):ポリエーテルエーテルケトン(溶融粘度;1.48kNsm-2。)
芳香族ポリエーテルケトン樹脂(2):ポリエーテルエーテルケトン(溶融粘度;1.19kNsm-2。)
芳香族ポリエーテルケトン樹脂(3):ポリエーテルエーテルケトン(溶融粘度;0.31kNsm-2。)
フッ素樹脂(1):テトラフルオロエチレン/ヘキサフルオロプロピレン共重合体(組成重量比;テトラフルオロエチレン/ヘキサフルオロプロピレン/パーフルオロ(プロピルビニルエーテル)=87.5/11.5/1.0。MFR;23g/10分。溶融粘度;0.55kNsm-2。)
フッ素樹脂(2):テトラフルオロエチレン/ヘキサフルオロプロピレン共重合体(組成重量比;テトラフルオロエチレン/ヘキサフルオロプロピレン/パーフルオロ(プロピルビニルエーテル)=87.5/11.5/1.0。MFR;60g/10分。溶融粘度;0.28kNsm-2。)
フッ素樹脂(3):テトラフルオロエチレン/ヘキサフルオロプロピレン共重合体(組成重量比;テトラフルオロエチレン/ヘキサフルオロプロピレン=88.5/11.5。MFR;6g/10分。溶融粘度;2.23kNsm-2。)
フッ素樹脂(4):ポリテトラフルオロエチレン(商品名:ルブロンL5、ダイキン工業(株)製。)
フッ素樹脂(5):エチレン/テトラフルオロエチレン共重合体(商品名:ネオフロンEP541、ダイキン工業(株)製。溶融粘度;2.27kNsm-2。)
芳香族ポリエーテルケトン樹脂(2)及びフッ素樹脂(1)を表1に示す割合(質量部)で予備混合を行い、二軸押出機(φ15mm、L/D=60)を使用して、シリンダー温度390℃、スクリュウ回転数300rpmの条件下で溶融混練し、樹脂組成物を製造した。得られた樹脂組成物を用いて、上記した方法で試験片を作製し、限界PV値、動摩擦係数、ノッチ付きアイゾッド強度の測定を行った。また、当該試験片にてフッ素樹脂(II)の平均分散粒子径及び最大分散粒子径を算出した。
芳香族ポリエーテルケトン樹脂(2)及びフッ素樹脂(1)を表1に示す割合(質量部)で予備混合を行い、二軸押出機(φ15mm、L/D=60)を使用して、シリンダー温度390℃、スクリュウ回転数500rpmの条件下で溶融混練し、樹脂組成物を製造した。得られた樹脂組成物を用いて、上記した方法で試験片を作製し、限界PV値、動摩擦係数、ノッチ付きアイゾッド強度の測定を行った。また、当該試験片にてフッ素樹脂(1)の平均分散粒子径及び最大分散粒子径を算出した。
芳香族ポリエーテルケトン樹脂(2)及びフッ素樹脂(1)を表1に示す割合(質量部)で予備混合を行い、二軸押出機(φ15mm、L/D=60)を使用して、シリンダー温度390℃、スクリュウ回転数300rpmの条件下で溶融混練し、樹脂組成物を製造した。得られた樹脂組成物を用いて、上記した方法で試験片を作製し、限界PV値、動摩擦係数、ノッチ付きアイゾッド強度の測定を行った。また、当該試験片にてフッ素樹脂(1)の平均分散粒子径及び最大分散粒子径を算出した。
芳香族ポリエーテルケトン樹脂(2)及びフッ素樹脂(3)を表1に示す割合(質量部)で予備混合を行い、二軸押出機(φ15mm、L/D=60)を使用して、シリンダー温度390℃、スクリュウ回転数500rpmの条件下で溶融混練し、樹脂組成物を製造した。得られた樹脂組成物を用いて、上記した方法で試験片を作製し、限界PV値、動摩擦係数、ノッチ付きアイゾッド強度の測定を行った。また、当該試験片にてフッ素樹脂(3)の平均分散粒子径及び最大分散粒子径を算出した。
芳香族ポリエーテルケトン樹脂(3)及びフッ素樹脂(1)を表1に示す割合(質量部)で予備混合を行い、二軸押出機(φ15mm、L/D=60)を使用して、シリンダー温度390℃、スクリュウ回転数500rpmの条件下で溶融混練し、樹脂組成物を製造した。得られた樹脂組成物を用いて、上記した方法で試験片を作製し、限界PV値、動摩擦係数、ノッチ付きアイゾッド強度の測定を行った。また、当該試験片にてフッ素樹脂(1)の平均分散粒子径及び最大分散粒子径を算出した。
芳香族ポリエーテルケトン樹脂(1)のみを使用して、上記した方法で試験片を作製し、限界PV値、動摩擦係数、ノッチ付きアイゾッド強度の測定を行った。
芳香族ポリエーテルケトン樹脂(1)と、フッ素樹脂(4)又はフッ素樹脂(5)とを表1に示す割合(質量部)で予備混合を行い、二軸押出機(φ15mm、L/D=60)を使用して、シリンダー温度390℃、スクリュウ回転数300rpmの条件下で溶融混練し、樹脂組成物を製造した。得られた樹脂組成物を用いて、上記した方法でプレスシートを作製し、限界PV値、動摩擦係数、ノッチ付きアイゾッド強度の測定を行った。また、プレスシートから超薄切片を切り出し、フッ素樹脂(4)又は(5)の平均分散粒子径及び最大分散粒子径を算出した。
芳香族ポリエーテルケトン樹脂(3)、フッ素樹脂(3)を表1に示す割合(質量部)で予備混合を行い、二軸押出機(φ15mm、L/D=60)を使用して、シリンダー温度390℃、スクリュウ回転数500rpmの条件下で溶融混練し、樹脂組成物を製造した。得られた樹脂組成物を用いて、上記した方法でプレスシートを作製し、限界PV値、動摩擦係数、ノッチ付きアイゾッド強度の測定を行った。また、プレスシートから超薄切片を切り出し、フッ素樹脂(3)の平均分散粒子径及び最大分散粒子径を算出した。
芳香族ポリエーテルケトン樹脂(1)、フッ素樹脂(2)を表1に示す割合(質量部)で予備混合を行い、二軸押出機(φ15mm、L/D=60)を使用して、シリンダー温度390℃、スクリュウ回転数300rpmの条件下で溶融混練し、樹脂組成物を製造した。得られた樹脂組成物を用いて、上記した方法でプレスシートを作製し、限界PV値、動摩擦係数、ノッチ付きアイゾッド強度の測定を行った。また、プレスシートから超薄切片を切り出し、フッ素樹脂(2)の平均分散粒子径及び最大分散粒子径を算出した。
芳香族ポリエーテルケトン樹脂(2)、フッ素樹脂(1)を表1に示す割合(質量部)で予備混合を行い、ベント式押出機(φ50mm、L/D=24)を使用して、シリンダー温度390℃、スクリュウ回転数25rpmの条件下で混合し、幅500mmのスリット台から押出し、130℃の引き取りロールで延伸し、25μmに延伸したフィルムを作成し、フッ素樹脂(1)の平均分散粒子径及び最大分散粒子径を算出した。
Claims (7)
- 芳香族ポリエーテルケトン樹脂(I)及びフッ素樹脂(II)を含む樹脂組成物であって、
フッ素樹脂(II)は、テトラフルオロエチレン及び下記の一般式(1):
CF2=CF-Rf1 (1)
(式中、Rf1は、-CF3又は-ORf2を表す。Rf2は、炭素数1~5のパーフルオロアルキル基を表す。)で表されるパーフルオロエチレン性不飽和化合物の共重合体であり、
芳香族ポリエーテルケトン樹脂(I)とフッ素樹脂(II)との質量比(I):(II)が95:5~50:50であり、
芳香族ポリエーテルケトン樹脂(I)とフッ素樹脂(II)との溶融粘度比(I)/(II)が0.3~5.0であり、
フッ素樹脂(II)が芳香族ポリエーテルケトン樹脂(I)中に粒子状に分散しており、フッ素樹脂(II)の平均分散粒子径が3.0μm未満であることを特徴とする樹脂組成物。 - フッ素樹脂(II)が芳香族ポリエーテルケトン樹脂(I)中に粒子状に分散しており、
フッ素樹脂(II)の平均分散粒子径が0.3μm未満であり、且つ最大分散粒子径が0.8μm以下である請求項1記載の樹脂組成物。 - フッ素樹脂(II)は、メルトフローレートが0.1~100g/10分である請求項1又は2に記載の樹脂組成物。
- 芳香族ポリエーテルケトン樹脂(I)は、ポリエーテルエーテルケトンである請求項1、2又は3に記載の樹脂組成物。
- 請求項1、2、3又は4に記載の樹脂組成物からなる成形品。
- 摺動部材として使用される請求項5に記載の成形品。
- シール材、ギア、アクチュエーター、ピストン、ベアリング又はブッシュである請求項5又は6に記載の成形品。
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- 2012-11-29 JP JP2013549202A patent/JPWO2013088964A1/ja active Pending
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EP2881430A4 (en) * | 2012-08-06 | 2015-08-05 | Daikin Ind Ltd | RESIN COMPOSITION AND ARTICLES |
US10294362B2 (en) | 2012-08-06 | 2019-05-21 | Daikin Industries, Ltd. | Resin composition and molded article |
WO2014024671A1 (ja) * | 2012-08-06 | 2014-02-13 | ダイキン工業株式会社 | 樹脂組成物及び成形品 |
CN105408422A (zh) * | 2013-07-25 | 2016-03-16 | 大金工业株式会社 | 热塑性树脂组合物和成型品 |
JP2015042740A (ja) * | 2013-07-25 | 2015-03-05 | ダイキン工業株式会社 | 熱可塑性樹脂組成物および成形品 |
WO2015012346A1 (ja) * | 2013-07-25 | 2015-01-29 | ダイキン工業株式会社 | 熱可塑性樹脂組成物および成形品 |
US10964444B2 (en) | 2013-07-25 | 2021-03-30 | Daikin Industries, Ltd. | Thermoplastic resin composition, and molded article thereof |
WO2016010127A1 (ja) * | 2014-07-18 | 2016-01-21 | ダイキン工業株式会社 | フィルム及びその製造方法 |
JP2016029164A (ja) * | 2014-07-18 | 2016-03-03 | ダイキン工業株式会社 | フィルム及びその製造方法 |
KR20170018944A (ko) | 2014-07-18 | 2017-02-20 | 다이킨 고교 가부시키가이샤 | 필름 및 그 제조 방법 |
CN106536631A (zh) * | 2014-07-18 | 2017-03-22 | 大金工业株式会社 | 膜及其制造方法 |
KR101903299B1 (ko) * | 2014-07-18 | 2018-10-01 | 다이킨 고교 가부시키가이샤 | 필름 및 그 제조 방법 |
US10113041B2 (en) | 2014-07-18 | 2018-10-30 | Daikin Industries, Ltd. | Film and method for producing same |
WO2020196243A1 (ja) * | 2019-03-27 | 2020-10-01 | ダイキン工業株式会社 | 樹脂組成物および成形品 |
JP2019183175A (ja) * | 2019-08-01 | 2019-10-24 | ダイキン工業株式会社 | 離型フィルム |
Also Published As
Publication number | Publication date |
---|---|
EP2778199A1 (en) | 2014-09-17 |
EP2778199A4 (en) | 2015-05-20 |
EP2778199B1 (en) | 2017-05-17 |
TW201336931A (zh) | 2013-09-16 |
US20140329968A1 (en) | 2014-11-06 |
JPWO2013088964A1 (ja) | 2015-04-27 |
CN103958608A (zh) | 2014-07-30 |
CN103958608B (zh) | 2016-08-17 |
KR20140105550A (ko) | 2014-09-01 |
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