Polyaryletherketone resin composition, molded article thereof, and method for producing polyaryletherketone resin composition

Abstract

To provide a polyaryletherketone resin material having improved load bearing capacity at high temperatures without compounding a reinforcing agent or a filler.SOLUTION: A polyaryletherketone resin composition comprising a first resin component and a second resin component. [First Resin Component] A polyaryletherketone having a glass transition temperature of 220 °C. or more and a weight-average molecular weight in the range of 2,000 or more and 1,000,000 or less. [Second Resin Component] A polyaryletherketone having a glass transition temperature of 100 °C. or more and less than 220 °C. and a weight average molecular weight in the range of 2,000 or more and 1,000,000 or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polyaryl ether ketone (PAEK) resin composition and its use, and more particularly to a PAEK resin composition obtained using bisphenol as a raw material and its use. [Background technology]

[0002] Polyaryletherketone (PAEK) resins, such as polyarylketone, polyetherketone (PEK), and polyetheretherketone (PEEK), offer highly desirable properties such as solvent resistance, flame retardancy, low wear rate, abrasion resistance, and high strength. In particular, PEEK is known as a crystalline PAEK and is used in a variety of fields. However, PEEK's relatively low glass transition temperature (Tg) limits its use under high temperature loads. This drawback can be ameliorated by adding glass fibers (Patent Document 1), carbon fibers (Patent Document 2), other reinforcing agents, and inorganic fillers (Patent Document 3). However, while these improvements improve one property, they adversely affect other properties. For example, adding fibers increases weight, reduces flowability, and introduces anisotropy into molded articles, affecting dimensional change. In some cases, fiber additives can disrupt the surface smoothness of molded parts, resulting in surface irregularities. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Chinese Patent Application Publication No. 108164923 [Patent Document 2] Chinese Patent Application Publication No. 111057346 [Patent Document 3] Japanese Patent Application Laid-Open No. 2012-97193 Summary of the Invention [Problem to be solved by the invention]

[0004] In view of the above problems, an object of the present invention is to provide a polyaryl ether ketone resin material having improved load-bearing capacity at high temperatures without incorporating a reinforcing agent or filler. [Means for solving the problem]

[0005] As a result of intensive research to solve the above-mentioned problems, the present inventors have found that a polyaryl ether ketone resin composition containing a specific polyaryl ether ketone and a different specific polyaryl ether ketone has improved load-bearing capacity at high temperatures without the need to incorporate a reinforcing agent or filler, and have completed the present invention.

[0006] The present invention is as follows. 1. A polyaryl ether ketone resin composition comprising a first resin component and a second resin component. [First resin component] A polyaryl ether ketone having a glass transition temperature of 220°C or higher and a weight average molecular weight in the range of 2,000 to 1,000,000. [Second resin component] A polyaryl ether ketone having a glass transition temperature of 100°C or higher but lower than 220°C and a weight average molecular weight of 2,000 or higher but 1,000,000 or lower. 2. The polyaryl ether ketone resin composition according to 1., wherein the first resin component and the second resin component are polyaryl ether ketones that are incompatible with each other. 3. The polyaryl ether ketone resin composition according to 1., wherein at least one of the first resin component and the second resin component is a crystalline polyaryl ether ketone. 4. The polyaryl ether ketone resin composition according to 1., wherein the weight ratio of the first resin component to the second resin component (first resin component:second resin component) is in the range of 1:99 to 99:1. 5. The polyaryl ether ketone resin composition according to 1., wherein the polyaryl ether ketone of the first resin component has a repeating unit represented by general formula (1A), (1B) or (1C). [ka] (In the formula, each R1 independently represents an alkyl group having 1 to 4 carbon atoms, and each n independently represents 0, 1, or 2.) [ka] (In the formula, each R1 independently represents an alkyl group having 1 to 4 carbon atoms, and each n independently represents 0, 1, or 2.) [ka] (In the formula, each R1 independently represents an alkyl group having 1 to 4 carbon atoms, and each n independently represents 0, 1, or 2.) 6. The polyaryl ether ketone resin composition according to 1., wherein the polyaryl ether ketone of the second resin component is a polyaryl ether ketone containing at least one of repeating units represented by formulas (4a) to (4e). [ka] 7. The polyaryl ether ketone resin composition according to 1., having a storage modulus at 200°C of 500 MPa or more. 8. A molded article made of the polyaryl ether ketone resin composition according to any one of 1. to 7. 9. A method for producing a polyaryl ether ketone resin composition, comprising mixing a first resin component and a second resin component in a molten state. [First resin component] A polyaryl ether ketone having a glass transition temperature of 220°C or higher and a weight average molecular weight in the range of 2,000 to 1,000,000. [Second resin component] A polyaryl ether ketone having a glass transition temperature of 100°C or higher but lower than 220°C and a weight average molecular weight of 2,000 or higher but 1,000,000 or lower. 10. The method for producing a polyaryl ether ketone resin composition according to 9., wherein the first resin component and the second resin component are polyaryl ether ketones that are incompatible with each other. 11. The method for producing a polyaryl ether ketone resin composition according to 9., wherein at least one of the first resin component and the second resin component is a crystalline polyaryl ether ketone. 12. The method for producing a polyaryl ether ketone resin composition according to 9., wherein the weight ratio of the first resin component to the second resin component is in the range of first resin component:second resin component=1:99 to 99:1. 13. The method for producing a polyaryl ether ketone resin composition according to 9., wherein the polyaryl ether ketone of the first resin component has a repeating unit represented by general formula (1A), (1B) or (1C). [ka] (In the formula, each R1 independently represents an alkyl group having 1 to 4 carbon atoms, and each n independently represents 0, 1, or 2.) [ka] (In the formula, each R1 independently represents an alkyl group having 1 to 4 carbon atoms, and each n independently represents 0, 1, or 2.) [ka] (In the formula, each R1 independently represents an alkyl group having 1 to 4 carbon atoms, and each n independently represents 0, 1, or 2.) 14. The method for producing a polyaryl ether ketone resin composition according to 9., wherein the polyaryl ether ketone of the second resin component is a polyaryl ether ketone containing one or more of the repeating units represented by formulas (4a) to (4e). [ka] 15. The method for producing a polyaryl ether ketone resin composition according to 9., wherein the storage modulus of the obtained polyaryl ether ketone resin composition at a temperature of 200°C is 500 MPa or more. [Effects of the Invention]

[0007] The polyaryl ether ketone resin composition of the present invention has improved load-bearing capacity at high temperatures. [Brief explanation of the drawings]

[0008] [Figure 1] 1 is a graph showing the results of measuring the dynamic viscoelasticity of the polyaryl ether ketone resin compositions obtained in Examples 1 and 2, the PEEK used in Comparative Example 1, and the PAEK having a repeating unit represented by formula (1A-1) used in Comparative Example 2. [Figure 2] 1 is a graph showing the results of measuring the dynamic viscoelasticity of the polyaryl ether ketone resin composition obtained in Example 3, the PEEK used in Comparative Example 1, and the PAEK having a repeating unit represented by formula (1B-1) used in Comparative Example 3. [Figure 3] 1 is a graph showing the results of measuring the dynamic viscoelasticity of the polyaryl ether ketone resin composition obtained in Example 4, the PEEK used in Comparative Example 1, and the PAEK having a repeating unit represented by formula (1C-1) used in Comparative Example 4. DETAILED DESCRIPTION OF THE INVENTION

[0009] <Polyaryletherketone (PAEK) resin composition of the present invention> The polyaryletherketone (PAEK) resin composition of the present invention comprises a first resin component and a second resin component. [First resin component] A polyaryl ether ketone having a glass transition temperature of 220°C or higher and a weight average molecular weight in the range of 2,000 to 1,000,000. [Second resin component] Polyaryl ether ketone having a glass transition temperature of 100°C or higher but lower than 220°C and a weight average molecular weight in the range of 2,000 or higher but 1,000,000 or lower. The inventors of the present invention presume that when the polyaryl ether ketone of the first resin component and the polyaryl ether ketone of the second resin component are incompatible with each other, in particular, the resin components in the resin composition obtained by mixing these components undergo phase separation, which is why the resin composition of the present invention exhibits improved load-bearing capacity at high temperatures. The mutual incompatibility of the polyaryl ether ketone of the first resin component and the polyaryl ether ketone of the second resin component can be confirmed by the presence of two glass transition points when differential scanning calorimetry (DSC) is performed on the resin composition. When at least one of the first resin component and the second resin component is a crystalline polyaryletherketone, phase separation of the resin components occurs in the resulting resin composition. It is preferable that the first resin component is a non-crystalline polyaryletherketone and the second resin component is a crystalline polyaryletherketone.

[0010] The weight ratio of the first resin component to the second resin component contained in the polyaryl ether ketone resin composition of the present invention is preferably in the range of 99:1 to 1:99 (first resin component:second resin component), more preferably in the range of 70:30 to 5:95, even more preferably in the range of 50:50 to 5:95, particularly preferably in the range of 30:70 to 5:95, and most preferably in the range of 20:80 to 5:95.

[0011] The storage modulus of the polyaryl ether ketone resin composition of the present invention at a temperature of 200°C is preferably 500 MPa or more. Since it is in this range, it has sufficient load-bearing capacity at high temperatures. The storage modulus at a temperature of 200°C is more preferably 600 MPa or more, even more preferably 800 MPa or more, particularly preferably 900 MPa or more, and most preferably 1000 MPa or more. The larger the storage modulus at 200°C, the better the load-bearing capacity at high temperatures. Therefore, there is no upper limit, but it may be 2000 MPa or less.

[0012] (First resin component) The first resin component according to the present invention is a polyaryl ether ketone (PAEK) having a glass transition temperature (Tg) of 220°C or higher and a weight-average molecular weight in the range of 2,000 to 1,000,000. Such a PAEK is obtained by a desalination polycondensation reaction of a dihalogen compound represented by general formula (2) with an aromatic dihydroxy compound in the presence of an alkali metal compound. The structure of the PAEK preferably has a repeating unit represented by general formula (1A), (1B), or (1C). The repeating unit in the PAEK structure may have a repeating unit other than the repeating unit represented by general formula (1A), (1B), or (1C), but preferably has only the repeating unit represented by general formula (1A), (1B), or (1C). [ka] (wherein X represents a halogen atom). [ka] (In the formula, each R1 independently represents an alkyl group having 1 to 4 carbon atoms, and each n independently represents 0, 1, or 2.) [ka] (In the formula, each R1 independently represents an alkyl group having 1 to 4 carbon atoms, and each n independently represents 0, 1, or 2.) [ka] (In the formula, each R1 independently represents an alkyl group having 1 to 4 carbon atoms, and each n independently represents 0, 1, or 2.) Each R1 independently represents an alkyl group having 1 to 4 carbon atoms, and is preferably a t-butyl group or a methyl group, with a methyl group being particularly preferred. The bonding position of R1 is preferably the ortho position relative to the position on the benzene ring to which the oxygen atom is bonded. Each n independently represents 0, 1 or 2, and is preferably 0 or 2.

[0013] (glass transition temperature) The glass transition temperature (Tg) of the PAEK of the first resin component according to the present invention is 220° C. or higher. The glass transition temperature (Tg) is more preferably 240° C. or higher, even more preferably 270° C. or higher, and particularly preferably 280° C. or higher.

[0014] (molecular weight) The first resin component according to the present invention has a weight average molecular weight (Mw) in the range of 2,000 to 1,000,000, preferably in the range of 10,000 to 500,000, more preferably in the range of 20,000 to 200,000, and particularly preferably in the range of 30,000 to 150,000. The ratio of weight average molecular weight (Mw) to number average molecular weight (Mn), Mw / Mn, is preferably in the range of 1.5 or more and 20 or less, more preferably in the range of 2 or more and 15 or less, even more preferably in the range of 2 or more and 10 or less, and particularly preferably in the range of 2 or more and 8 or less.

[0015] (reduced viscosity) The reduced viscosity of the PAEK of the first resin component according to the present invention is preferably 0.1 dL / g or more, more preferably 0.3 dL / g or more, and even more preferably 0.5 dL / g or more, as measured at 40°C of a 1.0 g / dL solution of the PAEK of the present invention in p-chlorophenol as a solvent.

[0016] (Production method of PAEK of the present invention) The method for producing the PAEK of the present invention, in which the glass transition temperature (Tg) of the first resin component is 220°C or higher, is not particularly limited. For example, the PAEK can be produced by subjecting a dihalogen compound represented by general formula (2) and an aromatic dihydroxy compound to a desalting polycondensation reaction in the presence of an alkali metal compound.

[0017] As a specific example, the reaction scheme for the production of PAEK is shown below, in which 4,4'-difluorobenzophenone (2a) is used as the halogen compound represented by general formula (2), 4,4'-(9-fluorenylidene)bis(2,6-dimethylphenol) (3A-1) is used as the aromatic dihydroxy compound represented by general formula (3A), and potassium carbonate is used as the alkali metal compound. [ka]

[0018] (Dihalogen compound represented by general formula (2)) Specific examples of the dihalogen compound represented by general formula (2) include 3,3'-difluorobenzophenone, 3,3'-dichlorobenzophenone, 3,3'-dibromobenzophenone, 3,3'-diiodobenzophenone, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, and 4,4'-diiodobenzophenone. Among these, 4,4'-difluorobenzophenone and 4,4'-dichlorobenzophenone are preferred, and 4,4'-difluorobenzophenone is particularly preferred.

[0019] (aromatic dihydroxy compounds) The aromatic dihydroxy compound is not limited as long as it is an aromatic hydroxy compound that can undergo a polycondensation reaction with the dihalogen compound represented by general formula (2) to form the first resin component, but is preferably an aromatic dihydroxy compound represented by general formula (3A), (3B) or (3C). [ka] (In the formula, R1 and n are defined as in general formula (1A).) [ka] (In the formula, R1 and n are defined as in general formula (1B).) [ka] (In the formula, R1 and n are defined as in general formula (1C).)

[0020] (Aromatic dihydroxy compound represented by general formula (3A)) In the aromatic dihydroxy compound represented by the general formula (3A), R1 and n are defined as in the general formula (1A), and the preferred embodiments are also the same. Specific examples of the aromatic dihydroxy compound represented by general formula (3A) include 4,4'-(9-fluorenylidene)bis(2,6-dimethylphenol), 4,4'-(9-fluorenylidene)bis(2,5-dimethylphenol), 4,4'-(9-fluorenylidene)bis(3,5-dimethylphenol), 4,4'-(9-fluorenylidene)bis(2-methylphenol), and 4,4'-(9-fluorenylidene)bis(3-methylphenol). Among these, 4,4'-(9-fluorenylidene)bis(2,6-dimethylphenol), 4,4'-(9-fluorenylidene)bis(2,5-dimethylphenol), and 4,4'-(9-fluorenylidene)bis(2-methylphenol) are preferred, and 4,4'-(9-fluorenylidene)bis(2,6-dimethylphenol) is particularly preferred.

[0021] (Aromatic dihydroxy compound represented by general formula (3B)) In the aromatic dihydroxy compound represented by the general formula (3B), R1 and n are defined as in the general formula (1B), and the preferred embodiments are also the same. Specific examples of the aromatic dihydroxy compound represented by general formula (3B) include 4,4'-(3,3,5-trimethylcyclohexylidene)bis(2,6-dimethylphenol), 4,4'-(3,3,5-trimethylcyclohexylidene)bis(2,5-dimethylphenol), 4,4'-(3,3,5-trimethylcyclohexylidene)bis(3,5-dimethylphenol), 4,4'-(3,3,5-trimethylcyclohexylidene)bis(2-methylphenol), 4,4'-(3,3,5-trimethylcyclohexylidene)bis(3-methylphenol), and 4,4'-(3,3,5-trimethylcyclohexylidene)bisphenol. Among these, 4,4'-(3,3,5-trimethylcyclohexylidene)bis(2,6-dimethylphenol), 4,4'-(3,3,5-trimethylcyclohexylidene)bis(2,5-dimethylphenol), 4,4'-(3,3,5-trimethylcyclohexylidene)bis(2-methylphenol), 4,4'-(3,3,5-trimethylcyclohexylidene)bisphenol are preferred, and 4,4'-(3,3,5-trimethylcyclohexylidene)bis(2,6-dimethylphenol), 4,4'-(3,3,5-trimethylcyclohexylidene)bis(2-methylphenol) and 4,4'-(3,3,5-trimethylcyclohexylidene)bisphenol are more preferred, 4,4'-(3,3,5-trimethylcyclohexylidene)bis(2,6-dimethylphenol) and 4,4'-(3,3,5-trimethylcyclohexylidene)bisphenol are even more preferred, and 4,4'-(3,3,5-trimethylcyclohexylidene)bis(2,6-dimethylphenol) is particularly preferred.

[0022] (Aromatic dihydroxy compound represented by general formula (3C)) In the aromatic dihydroxy compound represented by the general formula (3C), R1 and n are defined as in the general formula (1C), and the preferred embodiments are also the same. Specific examples of the aromatic dihydroxy compound represented by the general formula (3C) include 1,3-dihydro-3,3-bis(4-hydroxy-2,6-dimethylphenyl)-1-phenyl-2H-indol-2-one, 1,3-dihydro-3,3-bis(4-hydroxy-2,5-dimethylphenyl)-1-phenyl-2H-indol-2-one, 1,3-dihydro-3,3-bis(4-hydroxy-3 ... Examples thereof include 1,3-dihydro-3,3-bis(4-hydroxy-2,5-dimethylphenyl)-1-phenyl-2H-indol-2-one, 1,3-dihydro-3,3-bis(4-hydroxy-2-methylphenyl)-1-phenyl-2H-indol-2-one, 1,3-dihydro-3,3-bis(4-hydroxy-3-methylphenyl)-1-phenyl-2H-indol-2-one, and 1,3-dihydro-3,3-bis(4-hydroxyphenyl)-1-phenyl-2H-indol-2-one. Among these, 1,3-dihydro-3,3-bis(4-hydroxy-3,5-dimethylphenyl)-1-phenyl-2H-indol-2-one, 1,3-dihydro-3,3-bis(4-hydroxy-2,5-dimethylphenyl)-1-phenyl-2H-indol-2-one, 1,3-dihydro-3,3-bis(4-hydroxy-3-methylphenyl)-1-phenyl-2H-indol-2-one, and 1,3-dihydro-3,3-bis(4-hydroxyphenyl)-1-phenyl-2H-indol-2-one are preferred, and 1 ,3-dihydro-3,3-bis(4-hydroxy-3,5-dimethylphenyl)-1-phenyl-2H-indol-2-one, 1,3-dihydro-3,3-bis(4-hydroxy-3-methylphenyl)-1-phenyl-2H-indol-2-one, and 1,3-dihydro-3,3-bis(4-hydroxyphenyl)-1-phenyl-2H-indol-2-one are more preferred, and 1,3-dihydro-3,3-bis(4-hydroxy-3,5-dimethylphenyl)-1-phenyl-2H-indol-2-one is particularly preferred.

[0023] Any alkali metal compound can be used as long as it can convert the aromatic dihydroxy compound to an alkali metal salt, but usually, carbonates, hydrogen carbonates, hydroxides, etc. of alkali metals are preferably used, and carbonates are particularly preferred. Examples of the alkali metal include lithium, sodium, potassium, rubidium, and cesium, and among these, sodium and potassium are preferred, and potassium is particularly preferred.

[0024] A solvent can be used in the polycondensation reaction to obtain PAEK, and its use is preferred. Neutral polar solvents such as N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), dimethylimidazolidinone (DMI), dimethyl sulfoxide (DMSO), sulfolane, and diphenyl sulfone are preferred, but any solvent can be used without any problems as long as it dissolves the monomer and PAEK. The solvent may be used alone, or two or more types may be used in combination as a mixed solvent.

[0025] (Polycondensation reaction conditions) The amount of the dihalogen compound represented by general formula (2) used is usually in the range of 0.9 to 1.1 times by mole, preferably 0.95 to 1.06 times by mole, and more preferably 1.0 to 1.04 times by mole, relative to the amount of the aromatic dihydroxy compound. The amount of the alkali metal compound used is usually in the range of 1.0 to 3.0 times by mole, preferably 1.01 to 1.3 times by mole, relative to the amount of the aromatic dihydroxy compound. The reaction temperature is usually in the range of 150 to 350°C, preferably 180 to 250°C, and the reaction time is usually 1 to 60 hours, preferably 2 to 50 hours. These reactions are preferably carried out in an atmosphere of an inert gas such as nitrogen or argon. There is no limitation on the reaction pressure, and the reaction may be carried out at reduced pressure, atmospheric pressure, or elevated pressure, but the reaction is usually carried out at atmospheric pressure.

[0026] <Post-reaction treatment> The PAEK produced by the polycondensation reaction can be recovered by a commonly used method such as coagulation, solidification, washing, granulation, extraction, or solvent distillation. A method for treating the PAEK produced by the polycondensation reaction will now be described in more detail by way of example. A liquid containing the PAEK produced by the polycondensation reaction can be reprecipitated by mixing the liquid obtained by diluting the polymer-containing reaction liquid with a solvent, if necessary, with a solvent, to obtain a powdered PAEK. Examples of solvents used for reprecipitation include methanol, ethanol, acetone, methyl ethyl ketone, xylene, and toluene. Acetone and methanol are particularly preferred because of their ease of operation and ease of distillation recovery of the reaction solvent after washing. The powdered PAEK obtained by reprecipitation is preferably subjected to a washing step in which the powdered PAEK is washed to remove alkali metal salts such as potassium chloride produced in the desalting polycondensation reaction, the solvent used in the reaction, and the solvent used in the reprecipitation. For washing away alkali metal salts such as potassium chloride produced in the desalting polycondensation reaction, water is preferred, but acidic water containing low concentrations of hydrochloric acid, formic acid, oxalic acid, etc. may also be used. The conditions for this washing step may be appropriately selected, such as the amount of washing solvent used, the number of washings, and the washing temperature, depending on the amounts of the residual reaction solvent and residual alkali metal salts to be removed. After washing with water, the powder may be washed with, for example, methanol, ethanol, acetone, methyl ethyl ketone, xylene, or toluene, particularly acetone or methanol. The equipment used for washing may be a combination of a washing tank and a pressure filter or a centrifuge, or a multi-function filter that can perform washing, filtering, and drying in one device.

[0027] A drying step can be carried out to dry the powdered PAEK containing water and solvent obtained after the washing step. The conditions for this drying step may be any conditions that allow removal of moisture at a temperature below the melting point of the polycondensation reaction product. To minimize contact with air, the step is preferably carried out in an inert gas (nitrogen, argon, etc.) atmosphere, in an inert gas stream, or under reduced pressure. The dryer may be a known device such as an evaporator, a tray oven, or a tumbler.

[0028] (Second resin component) The second resin component is a polyaryl ether ketone having a glass transition temperature (Tg) in the range of 100°C or higher and lower than 220°C. Examples of such polyaryl ether ketones (PAEKs) having a glass transition temperature (Tg) in the range of 100°C or higher and lower than 220°C include PAEKs containing one or more of the repeating units represented by formulas (4a) to (4e). [ka] The PAEKs containing repeating units represented by formulas (4a) to (4e) are polyether ketone (PEK), polyether ether ketone (PEEK), polyether ketone ether ketone ketone (PEKEKK), polyether ether ether ketone (PEEEK), and polyether ketone ketone (PEKK), respectively. Specific examples of polyetherketone (PEK) products include Victrex's HT G22 and HT G45 products. Specific examples of polyetheretherketone (PEEK) products include Victrex's Victrex Powder series and Victrex Granules series, Daicel-Evonik's VestaKeep series, and Solvay Specialty Polymers' KetaSpire PEEK series. Specific examples of polyetherketoneetherketoneketone (PEKEKK) products include Victrex's STG45 product. Specific examples of polyetheretheretherketone (PEEEK) products include Arkema's KEPSTAN 6002 product.

[0029] <Method for producing polyaryletherketone (PAEK) resin composition of the present invention> The polyaryletherketone (PAEK) resin composition of the present invention can be produced by using the first resin component and the second resin component in the above weight ratio and mixing them in a molten state. The temperature during mixing can be adjusted appropriately depending on the melting points of the first and second resin components used, but can be in the range of 350 to 450°C, for example. The mixing may be carried out in an air atmosphere or in an oxygen-free nitrogen atmosphere, but is preferably carried out in a nitrogen atmosphere in order to suppress oxidation degradation due to oxygen.

[0030] The polyaryl ether ketone resin composition of the present invention can be molded into various articles by known molding and processing methods for thermoplastic resins. Preferred molding and processing methods include, for example, injection molding, blow molding, compression molding, profile extrusion, sheet or film extrusion, sintering, and gas-assisted molding. Examples of such shaped articles include molding materials in the form of pellets, chips, etc., and devices molded with snap-fit ​​connectors, such as membranes, tubing, fibers, composites, semiconductor process tools, wire coatings and jackets, fluid handling components, cookware, food service items, medical devices, trays, plates, handles, helmets, animal cages, electrical connectors, electrical equipment housings, engine parts, automotive parts, aerospace equipment parts, bearings, light sockets and reflectors, electric motor parts, power distribution equipment, communications equipment, computers, etc. Additionally, the polyaryletherketone resin composition can be used as a coating material, such as a powder coating material. The polyaryletherketone resin composition can also be extruded into rods or slabs that can be used to form articles by machining.

[0031] The polyaryl ether ketone resin composition of the present invention may be blended with various additives, such as colorants such as titanium dioxide, zinc sulfide, and carbon black; stabilizers such as hindered phenols, phosphites, phosphonites, thioesters, and mixtures thereof; mold release agents; lubricants; metal deactivators; plasticizers; nucleating agents such as talc; wear-resistant additives such as fluoropolymers and metal sulfides; flame retardants; smoke suppressants; drip-proofing agents; color improvers such as phosphonate or phosphite compounds or mixtures thereof; and ultraviolet stabilizers. The effective amounts and blending methods of the above-mentioned additives are well known in the art and can be blended by conventional methods. The effective amount of additives varies widely, but is blended in the range of 0.01 to 30% by weight based on the weight of the first resin component and the second resin component used. [Example]

[0032] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0033] The analytical method in the present invention is as follows. <Analysis method> 1. Measurement of glass transition temperature (Tg) and melting point The glass transition temperatures and melting points of the PAEK obtained in the synthesis examples described below, the PAEK resin compositions obtained in the examples, and the PEEK used in the comparative examples were measured using the following apparatus and under the following conditions. Measurement equipment: DSC7020 (Hitachi) Pan: Aluminum Atmosphere: N2 Heating rate: 10℃ / min. Analysis method: [Glass transition temperature] 2 nd Glass transition temperature (intersection of the baseline and tangent line) [Melting point] 2 nd The melting point was determined as the intersection of the baseline and the tangent to the endothermic peak appearing around 350°C during heating. 2.Molecular weight measurement The molecular weights of the PAEK resin compositions obtained in the examples and the PAEKs obtained in the synthesis examples were measured by gel permeation chromatography (GPC) using the following apparatus and conditions. Equipment: 515 HPLC pump, 717plus automatic insertion device, 2487 UV-visible detector (Waters) Column / Temperature: 2 x PLgel 5μMIXED-D, 7.5 x 300 mm (Agilent Technologies) / 40°C Mobile phase: HPLC-grade chloroform Flow rate: 1.0mL / min. Injection volume: 2.5uL Detection: UV-visible detector 254 nm Column calibration: Monodisperse PS; EasiCal Type PS-1 polystyrene (Agilent Technologies) Molecular weight calibration: PS conversion 3.Measurement of reduced viscosity The PAEK resin compositions obtained in the examples and the PAEK powders obtained in the synthesis examples were dissolved in p-chlorophenol to prepare solutions with a concentration of 1.0 g / dL, and the viscosity at 40°C was measured. 4. Dynamic Mechanical Analysis (DMA) <Preparation of test specimens for dynamic mechanical analysis (DMA)> Test pieces were prepared using the polyaryletherketone resin compositions obtained in Examples 1 to 4 and the PAEK used in the Comparative Examples as the material resins using a Mini Test Press MP-2FH (manufactured by Toyo Seiki Co., Ltd.) The molding was performed by degassing several times at a temperature of 360°C and a pressure of 1 to 5 MPa, followed by compression bonding at a temperature of 360°C and a pressure of 12 MPa for 5 minutes. <Measurement equipment and conditions> Equipment: DMA0850-00600 (Hitachi) Heating rate: 3℃ / min. Vibration frequency: 1Hz Test piece size: length 10 mm x width 2.0 ± 0.5 mm x thickness 0.5 to 0.9 mm 5. Compatibility evaluation When the number of glass transition points observed in the glass transition temperature measurement was two, the first resin component and the second resin component used in the resin composition were evaluated as being incompatible with each other, and when the number of glass transition points observed was one, they were evaluated as being compatible with each other.

[0034] <Synthesis example 1: PAEK-1A-1> A powder of PAEK (PAEK-1A-1) having a repeating unit represented by formula (1A-1) was synthesized by the reaction shown in the following reaction formula. [ka] In a 500 mL four-necked reactor equipped with a Dean-Stark tube filled with toluene, a stirrer, and a nitrogen inlet, 27 g of 4,4'-difluorobenzophenone represented by formula (2a), 50 g of 4,4'-(9-fluorenylidene)bis(2,6-dimethylphenol) represented by formula (3A-1), 20 g of potassium carbonate, and 200 g of N-methylpyrrolidone (NMP) were added and dissolved at room temperature under nitrogen flow. The reactor was then heated to 200°C over 1 hour, after which a small amount of toluene was added, the mixture was refluxed, and polymerized at 200°C for 10 hours. After the reaction was complete, the reaction mixture was cooled to room temperature, diluted with 156 g of NMP, and added to 2850 g of methanol for reprecipitation. The precipitate was filtered off, and the resulting powder was suspended and washed in 1000 g of a 1.4% aqueous oxalic acid solution. It was then washed repeatedly with hot water until the water became neutral, and then washed with methanol. The washed powder was dried under reduced pressure at 150 °C for 12 hours, yielding 65 g of a powder of PAEK (PAEK-1A-1) (Mw: 76.856, Mw / Mn: 5.5) having a repeating unit represented by formula (1A-1) in an 87% yield. The reduced viscosity of the resulting PAEK was 0.63 dL / g. Differential scanning calorimetry of the resulting PAEK revealed that the glass transition temperature (Tg) was 286°C and no melting point was observed.

[0035] <Synthesis example 2: PAEK-1B-1> A powder of PAEK (PAEK-1B-1) having a repeating unit represented by formula (1B-1) was synthesized by the reaction shown in the following reaction formula. [ka] In a 500 mL four-necked reactor equipped with a Dean-Stark tube filled with toluene, a stirrer, and a nitrogen inlet, 31 g of 4,4'-difluorobenzophenone represented by formula (2a), 50 g of 4,4'-(3,3,5-trimethylcyclohexylidene)bis(2,6-dimethylphenol) represented by formula (3B-1), 17 g of sodium carbonate, and 240 g of NMP were added and dissolved at room temperature under nitrogen flow. The reactor was then heated to 200 °C over 1 hour, after which a small amount of toluene was added, the mixture was refluxed, and polymerized at 200 °C for 50 hours. After the reaction was complete, the reaction mixture was cooled to room temperature and diluted with 180 g of NMP. The resulting solution was added to 3200 g of methanol for reprecipitation. The precipitate was filtered off, and the resulting powder was suspended and washed in 1000 g of a 1.4% aqueous oxalic acid solution. It was then washed repeatedly with hot water until the water became neutral, and then with methanol. The washed powder was dried under reduced pressure at 150 °C for 12 hours to obtain 65 g of a powder of PAEK (PAEK-1B-1) (Mw: 51,200, Mw / Mn: 3.0) having a repeating unit represented by formula (1B-1) in an 85% yield. The reduced viscosity of the resulting PAEK was 0.45 dL / g. Differential scanning calorimetry of the resulting PAEK revealed that the glass transition temperature (Tg) was 243°C, and no melting point was observed.

[0036] <Synthesis example 3: PAEK-1C-1> A powder of PAEK (PAEK-1C-1) having a repeating unit represented by formula (1C-1) was synthesized by the reaction shown in the following reaction formula. [ka] A 500 mL four-necked reactor equipped with a Dean-Stark tube, a stirrer, and a nitrogen inlet tube filled with toluene was charged with 34 g of 4,4'-difluorobenzophenone represented by formula (2a), 19 g of 1,3-dihydro-3,3-bis(4-hydroxyphenyl)-1-phenyl-2H-indol-2-one represented by formula (3C-1), 11 g of sodium carbonate, and 161 g of NMP. These were dissolved at room temperature while passing nitrogen through the reactor. The reactor was then heated to 200 °C over 1 hour, after which a small amount of toluene was added and the mixture was refluxed and polymerized at 200 °C for 7 hours. After completion of the reaction, the product was cooled to room temperature and diluted with 107 g of N-methylpyrrolidone. The solution was reprecipitated in 2150 g of methanol. The precipitate was filtered, suspended and washed in 800 g of 1.4% aqueous oxalic acid solution, washed with hot water until neutral, and then washed with methanol. After drying under reduced pressure at 150°C for 12 hours, 44 g of a powder of PAEK (PAEK-1C-1) having a repeating unit represented by formula (1C-1) (Mw: 49,500, Mw / Mn: 3.1) was obtained in a yield of 87%. The reduced viscosity of the resulting PAEK was 0.56 dL / g. Differential scanning calorimetry of the obtained PAEK revealed that the glass transition point (Tg) was 240°C and no melting point was observed.

[0037] <Examples 1 to 4> PAEK resin compositions were produced by polymer blending the PAEK obtained in Synthesis Examples 1 to 3 as the first resin component and polyether ether ketone (hereinafter referred to as PEEK) sold by Victrex as VICTREX 450G as the second resin component in the parts by mass shown in Table 1. Polymer blending was carried out using the following apparatus and conditions. (Polymer blending equipment and conditions) Equipment: Circulation mixer [XploreMC15HT] (manufactured by Xplore Instrument) Temperature / Time: 370℃ / 5min. Rotation speed: 100 rpm Screw shape: Conical twin screw Mixing environment: Under N2 flow The PAEK resin composition obtained by polymer blending was subjected to compatibility evaluation and differential scanning calorimetry measurement using the methods described above. The results, including the number of glass transition points exhibited, glass transition temperatures, and melting points, are shown in Table 1. Furthermore, test specimens for dynamic viscoelasticity measurement were prepared from the obtained PAEK resin composition, and the dynamic viscoelasticity measurement was also performed using the methods described above. The results are shown in Table 2.

[0038] <Comparative Example 1> Using commercially available PEEK450G (manufactured by Victrex) (PEEK), test pieces for compatibility evaluation, differential scanning calorimetry, and dynamic viscoelasticity measurement were prepared and dynamic viscoelasticity measurement was performed in the same manner as in Examples 1 to 4. The results are shown in Tables 1 and 2.

[0039] <Comparative Examples 2 to 4> Using the PAEKs obtained in Synthesis Examples 1 to 3, test pieces for compatibility evaluation, differential scanning calorimetry, and dynamic viscoelasticity measurement were prepared and dynamic viscoelasticity measurement was performed in the same manner as in Examples 1 to 4. The results are shown in Tables 1 and 2.

[0040] [Table 1]

[0041] The results in Table 1 reveal that the PAEK resin compositions obtained in Examples 1 to 4 exhibit two glass transition points, which indicates that the PAEK of the first resin component and the PAEK of the second resin component are incompatible with each other. Furthermore, the PAEK resin compositions obtained in Examples 1 to 4 have melting points, unlike the PAEKs not blended with polymers in Comparative Examples 2 to 4. This is thought to be a result suggesting that these are resin materials that retain the crystallinity of PEEK.

[0042] [Table 2]

[0043] The dynamic viscoelasticity measurement results of the PAEK resin compositions obtained in Examples 1 and 2, the PEEK used in Comparative Example 1, and the PAEK having a repeating unit represented by formula (1A-1) used in Comparative Example 2 are summarized in FIG. 1. The storage modulus of the PEEK used in Comparative Example 1 significantly decreased from 1646 MPa to 223 MPa at temperatures ranging from 150°C to 200°C. The storage modulus of the PAEK used in Comparative Example 2 did not decrease significantly until around 280°C in FIG. 1, but as shown in Table 2, it decreased rapidly from 1510 MPa to 101 MPa from 275°C to 296°C. In contrast, it was revealed that the storage modulus of the PAEK resin composition obtained in Example 1 was higher than that of the PEEK used in Comparative Example 1 up to 296°C, which is the upper limit of the measurement temperature range. It was also revealed that the storage modulus of the PAEK resin composition obtained in Example 1 did not decrease abruptly as in the PAEK used in Comparative Example 2, but rather decreased gradually. Furthermore, it was revealed that at 296°C, which is the upper limit of the measurement temperature range, the storage modulus of the PAEK resin composition obtained in Example 1 was 133 MPa, which was higher than the 101 MPa of the PAEK used in Comparative Example 2. Furthermore, the storage modulus of the PAEK used in Comparative Example 2 does not decrease significantly up to 280°C in Figure 1, but begins to decrease rapidly above 280°C. The rate of decrease in storage modulus per degree Celsius in the range from 275°C to 296°C is large, at 67 MPa / °C. In contrast, it was revealed that the storage modulus of the PAEK resin composition obtained in Example 2 was higher up to 280°C than that of the PEEK used in Comparative Example 1. Furthermore, the storage modulus of the PAEK resin composition obtained in Example 2 maintained a high value up to 275°C in Figure 1. Although it decreased rapidly above 275°C, unlike the PAEK used in Comparative Example 2, the decrease slowed once above 275°C, and the rate of decrease in storage modulus per degree Celsius in the range from 275°C to 296°C was small, at 11 MPa / °C.

[0044] The dynamic viscoelasticity measurement results of the PAEK resin composition obtained in Example 3, the PEEK used in Comparative Example 1, and the PAEK having a repeating unit represented by formula (1B-1) used in Comparative Example 3 are summarized in FIG. 2. The storage modulus of the PAEK used in Comparative Example 3 does not decrease significantly up to 250°C in Fig. 2, but begins to decrease rapidly above 250°C and continues to decrease to less than 10 MPa. In the range from 250°C to 275°C, the rate of decrease in storage modulus per degree Celsius is as large as 42 MPa / °C. In contrast, it was revealed that the storage modulus of the PAEK resin composition obtained in Example 3 was higher up to 260°C than that of the PEEK used in Comparative Example 1. Furthermore, the storage modulus of the PAEK resin composition obtained in Example 3 maintained a high value up to 250°C in Figure 2. Although the storage modulus dropped sharply at temperatures above 250°C, unlike the PAEK used in Comparative Example 3, the drop once slowed down at temperatures above 250°C, and the rate of drop in storage modulus per degree Celsius in the range from 250°C to 275°C was found to be small at 17 MPa / °C.

[0045] The dynamic viscoelasticity measurement results of the PAEK resin composition obtained in Example 4, the PEEK used in Comparative Example 1, and the PAEK having a repeating unit represented by formula (1C-1) used in Comparative Example 4 are summarized in FIG. 3. The storage modulus of the PAEK used in Comparative Example 4 does not decrease significantly up to 240°C in FIG. 3, but decreases rapidly above 240°C, dropping to less than 10 MPa. In contrast, it was revealed that the storage modulus of the PAEK resin composition obtained in Example 4 was higher up to 240°C than that of the PEEK used in Comparative Example 1. Furthermore, the storage modulus of the PAEK resin composition obtained in Example 4 maintained a high value up to 240°C in Figure 3. Although the storage modulus dropped sharply at temperatures higher than 240°C, it was revealed that, unlike the PAEK used in Comparative Example 4, the drop once became gentler at temperatures higher than 240°C.

[0046] From the above, it has become clear that the PAEK resin composition of the present invention is a resin material having improved load-bearing capacity at high temperatures without the need for blending a reinforcing agent or filler.

Claims

1. A polyaryl ether ketone resin composition comprising a first resin component and a second resin component. [First resin component] A polyaryl ether ketone having a glass transition temperature of 220°C or higher and a weight average molecular weight in the range of 2,000 to 1,000,000. [Second Resin Component] A polyaryl ether ketone having a glass transition temperature of 100°C or higher but lower than 220°C and a weight average molecular weight of 2,000 or higher but 1,000,000 or lower.

2. The polyaryl ether ketone resin composition according to claim 1 , wherein the first resin component and the second resin component are polyaryl ether ketones that are incompatible with each other.

3. The polyaryl ether ketone resin composition according to claim 1, wherein at least one of the first resin component and the second resin component is a crystalline polyaryl ether ketone.

4. The polyaryl ether ketone resin composition according to claim 1, wherein the weight ratio of the first resin component to the second resin component is in the range of first resin component:second resin component=1:99 to 99:

1.

5. 2. The polyaryl ether ketone resin composition according to claim 1, wherein the polyaryl ether ketone of the first resin component has a repeating unit represented by general formula (1A), (1B) or (1C). 【Chemistry 1】 (In the formula, R １ each independently represents an alkyl group having 1 to 4 carbon atoms, and each n independently represents 0, 1, or 2. 【Chemistry 2】 (In the formula, R １ each independently represents an alkyl group having 1 to 4 carbon atoms, and each n independently represents 0, 1, or 2. 【Transformation 3】 (In the formula, R １ each independently represents an alkyl group having 1 to 4 carbon atoms, and each n independently represents 0, 1, or 2.

6. The polyaryl ether ketone resin composition according to claim 1, wherein the polyaryl ether ketone of the second resin component is a polyaryl ether ketone containing any one or more of the repeating units represented by formulas (4a) to (4e): 【Chemistry 4】

7. The polyaryl ether ketone resin composition according to claim 1, wherein the polyaryl ether ketone resin composition has a storage modulus at a temperature of 200°C of 500 MPa or more.

8. A molded article made from the polyaryl ether ketone resin composition according to any one of claims 1 to 7.

9. A method for producing a polyaryl ether ketone resin composition, comprising mixing a first resin component and a second resin component in a molten state. [First resin component] A polyaryl ether ketone having a glass transition temperature of 220°C or higher and a weight average molecular weight in the range of 2,000 to 1,000,000. [Second Resin Component] A polyaryl ether ketone having a glass transition temperature of 100°C or higher but lower than 220°C and a weight average molecular weight of 2,000 or higher but 1,000,000 or lower.

10. The method for producing a polyaryl ether ketone resin composition according to claim 9, wherein the first resin component and the second resin component are polyaryl ether ketones that are incompatible with each other.

11. The method for producing a polyaryl ether ketone resin composition according to claim 9, wherein at least one of the first resin component and the second resin component is a crystalline polyaryl ether ketone.

12. The method for producing a polyaryl ether ketone resin composition according to claim 9, wherein the weight ratio of the first resin component to the second resin component is in the range of first resin component:second resin component=1:99 to 99:

1.

13. The method for producing a polyaryl ether ketone resin composition according to claim 9, wherein the polyaryl ether ketone of the first resin component has a repeating unit represented by general formula (1A), (1B) or (1C). 【Transformation 5】 (In the formula, R １ each independently represents an alkyl group having 1 to 4 carbon atoms, and each n independently represents 0, 1, or 2. 【Transformation 6】 (In the formula, R １ each independently represents an alkyl group having 1 to 4 carbon atoms, and each n independently represents 0, 1, or 2. 【Transformation 7】 (In the formula, R １ each independently represents an alkyl group having 1 to 4 carbon atoms, and each n independently represents 0, 1, or 2.

14. The polyaryl ether ketone of the second resin component is a polyaryl ether ketone containing any one or more repeating units represented by formulas (4a) to (4e). The method for producing a polyaryl ether ketone resin composition according to claim 9. 【Transformation 8】

15. The method for producing a polyaryl ether ketone resin composition according to claim 9, wherein the storage modulus of the obtained polyaryl ether ketone resin composition at a temperature of 200°C is 500 MPa or more.

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