Melt-extrusion-molded poly(phenylene ether) body and production method therefor

Abstract

The purpose of the present invention is to provide: a melt-extrusion-molded poly(phenylene ether) body which dissolves in solvents and, after having dissolved in the solvents, produces less insoluble matter; and a production method for the melt-extrusion-molded poly(phenylene ether) body. This melt-extrusion-molded poly(phenylene ether) body includes a poly(phenylene ether) component, and is characterized in that: the poly(phenylene ether) component has, among consecutive repeating units arranged by para-position bonding, a dislocation structure connected by ortho-position bonding, the amount of the dislocation structure being 3.0 mol% or larger with respect to all the poly(phenylene ether) structural units in the poly(phenylene ether) component; and that in an examination by infrared spectroscopy, the absorbance height ratio (C / B) between the absorbance height B at a wavenumber of 1,600 cm-1 assignable to skeletal vibration due to stretching between carbon atoms of the benzene ring and the absorbance height C at a wavenumber of 1,650 cm-1 assignable to C=O stretching vibration is 0.04 or less.

Description

Polyphenylene ether melt extruded article and method for producing the same

[0001] The present invention relates to a polyphenylene ether melt extruded article and a method for producing the same.

[0002] Polyphenylene ether (hereinafter also referred to as "PPE") is widely used as a material for products and components in the electrical and electronic, automotive, and food and packaging fields, as well as in various other industrial materials, due to its excellent high-frequency properties, flame retardancy, and heat resistance. In particular, in recent years, its low dielectric properties and heat resistance have led to its application as a modifier in various applications, including electrical and electronic applications such as substrate materials.

[0003] However, generally speaking, high molecular weight PPEs (polyethylene polymers) with repeating units derived from monovalent phenols, such as 2,6-dimethylphenol, are soluble in highly toxic solvents like chloroform, but poorly soluble in aromatic solvents such as toluene, which are known as good solvents, and insoluble in ketone solvents such as methyl ethyl ketone. Therefore, for example, when used as a wiring board material, handling with resin varnish solutions such as toluene or methyl ethyl ketone was difficult.

[0004] As a composition containing PPE, for example, a resin composition is known that includes a low molecular weight PPE having a PPE portion in its molecular structure and having at least one p-ethenylbenzyl group or m-ethenylbenzyl group at the end of this molecular structure, and a crosslinking curing agent (see, for example, Patent Document 1).

[0005] Patent No. 4211784

[0006] Patent Document 1 describes dissolving PPE in a solvent such as toluene. However, it has now become clear that even when PPE can be dissolved in a solvent, a certain amount of insoluble material may remain after dissolution. The presence of such insoluble material can lead to defects such as appearance defects in the final product formed using the PPE solution.

[0007] Therefore, the object of the present invention is to provide a polyphenylene ether melt extruded molded article that dissolves in a solvent and has a small amount of insoluble matter when dissolved in a solvent, and a method for producing a polyphenylene ether melt extruded molded article.

[0008] The inventors of the present invention conducted thorough research on polyphenylene ether and found that the above problems could be solved by using a polyphenylene ether melt extruded molded article having the following configuration, thus completing the present invention.

[0009] In other words, the present invention relates to a polyphenylene ether melt extruded molded article containing a polyphenylene ether component, wherein the polyphenylene ether component is a polyphenylene ether component having a rearrangement structure in which ortho bonds are connected within repeating units that are continuous by para bonds, the amount of the rearrangement structure is 3.0 mol% or more relative to the total polyphenylene ether structural units in the polyphenylene ether component, and the wavenumber is 1600 cm², which originates from skeletal vibrations due to expansion and contraction between carbon atoms of the benzene ring, as measured by infrared spectroscopy. －１ Absorbance height B and C = O, derived from stretching vibration (ketone) wavenumber 1650 cm⁻¹ －１ The present invention relates to a polyphenylene ether melt extruded molded article characterized in that the ratio of absorbance height C to the absorbance height (C / B) is 0.04 or less.

[0010] It is preferable that the amount of insoluble matter when the polyphenylene ether molten extruded molded body is dissolved in toluene under the following conditions is 15% by mass or less. (Method for measuring the amount of insoluble matter) Dissolve the polyphenylene ether molten extruded molded body in toluene at 40°C to prepare a solution with a solid content of 10% by mass, and let it stand for 6 hours. Then, filter the solution and measure the amount of insoluble matter (Ag) that did not dissolve in toluene. Calculate the amount of insoluble matter using the following formula: Amount of insoluble matter (mass%) = (A / Amount of polyphenylene ether molten extruded molded body used (g)) × 100

[0011] It is preferable that the polyphenylene ether component content is 95% by mass or more of the total components forming the polyphenylene ether melt extruded molded article.

[0012] The repeating units that are continuous due to the para-position bonding are represented by the following general formula (1): (In the formula, R １ , R ２ are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and R ３ are each independently a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent), and the rearrangement structure is represented by the following general formula (2): (In the formula, R １ , R ２ are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, R ３ are each independently a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and R ３ ' represents a divalent group obtained by removing one hydrogen atom from the above R ３ ), and it is preferably a structure represented by this formula.

[0013] It is preferable that the polyphenylene ether melt extrusion molded body is polyphenylene ether pellets.

[0014] Further, the present invention relates to a method for producing the polyphenylene ether melt extrusion molded body, which has a step of melt extruding a polyphenylene ether as a raw material by an extruder equipped with a cylinder, a screw, and an extrusion nozzle, and is characterized in that the nozzle hole diameter of the extrusion nozzle is 2 mm or less.

[0015] It is preferable to perform melt extrusion at an extrusion temperature of 350°C or lower.

[0016] It is preferable that the peripheral speed of the screw is 10 m / min or more.

[0017] High molecular weight PPE components usually have low solubility in solvents. In particular, when the PPE component is contained in a high content or when the PPE component is contained alone, it has been considered difficult to dissolve in solvents such as toluene. Also, even when it can be dissolved in a solvent, there may be many insoluble substances that do not dissolve in the solvent. The PPE melt-extruded molded body of the present invention contains a PPE component having a dislocation structure (hereinafter also referred to as a methylene bridge dislocation structure (MBR)) connected by an ortho-position bond in a repeating unit continuous with a para-position bond. By measurement using infrared spectroscopy, the absorbance height ratio (C / B) of the absorbance height B at a wavenumber of 1600 cm －１ derived from the skeletal vibration due to the stretching and contraction between carbon atoms of the benzene ring and the absorbance height C at a wavenumber of 1650 cm －１ derived from the C=O stretching vibration (ketone) is 0.04 or less, so that the solubility in a solvent is improved and the amount of insoluble substances when dissolved in a solvent is reduced.

[0018] It is a cross-sectional view schematically showing an embodiment of a method for manufacturing a PPE melt-extruded molded body of the present invention.

[0019] 1. PPE melt-extruded molded body The PPE melt-extruded molded body of the present invention contains a PPE component, and the PPE component is a PPE component having a dislocation structure connected by an ortho-position bond in a repeating unit continuous with a para-position bond. The amount of the dislocation structure is 3.0 mol% or more with respect to all PPE structural units in the PPE component. By measurement using infrared spectroscopy, the absorbance height ratio (C / B) of the absorbance height B at a wavenumber of 1600 cm －１ derived from the skeletal vibration due to the stretching and contraction between carbon atoms of the benzene ring and the absorbance height C at a wavenumber of 1650 cm －１ derived from the C=O stretching vibration (ketone) is 0.04 or less.

[0020] The PPE melt-extruded molded body of the present invention has an absorbance height ratio (C / B) of the absorbance height B at a wavenumber of 1600 cm －１ derived from the skeletal vibration due to the stretching and contraction between carbon atoms of the benzene ring and the absorbance height C at a wavenumber of 1650 cm －１ derived from the C=O stretching vibration (ketone) of 0.04 or less.

[0021] Wavenumber 1650 cm⁻¹ originates from C=O stretching vibration (ketone). －１ The peak is a peak originating from the surface oxidation of the PPE melt extruded molded product. That is, the more advanced the surface oxidation of the PPE melt extruded molded product, the larger the C / B value becomes. In this invention, the peaks originating from skeletal vibrations due to expansion and contraction between carbon atoms of the benzene ring and the peaks originating from C=O stretching vibrations (ketones) are considered to be at a wavelength of 1600 ± 10 cm, taking into account the measurement error of infrared spectroscopy. －１ , 1650 ± 10 cm －１ This is the peak within the specified range.

[0022] The absorbance height ratio (C / B) is 0.040 or less, preferably 0.035 or less, from the viewpoint of solvent solubility and suppression of insoluble matter when dissolved in a solvent. The smaller the absorbance height ratio, the better, and ideally it is preferably 0.

[0023] The polyphenylene ether melt-extruded molded article of the present invention can have an insoluble matter content of 15% by mass or less, preferably 12% by mass or less, and more preferably 10% by mass or less, as measured under the following conditions. The smaller the amount of insoluble matter, the better, and ideally, it is preferable to have no insoluble matter (0% by mass). (Method for measuring the amount of insoluble matter) The polyphenylene ether melt-extruded molded article is dissolved in toluene at 40°C to prepare a solution with a solid content concentration of 10% by mass, and left to stand for 6 hours. Then, the solution is filtered and the amount of insoluble matter (Ag) that did not dissolve in toluene is measured. The amount of insoluble matter is calculated using the following formula: Amount of insoluble matter (mass%) = (A / Amount of polyphenylene ether melt-extruded molded article used (g)) × 100

[0024] <PPE component> The PPE component used in the present invention includes PPE having a rearrangement structure connected by ortho bonds within a repeating unit that is connected by para bonds. Here, "rearrangement structure connected by ortho bonds" refers to a structure in which a continuous side chain is formed by connecting by ortho bonds to a part of the repeating unit that is connected by para bonds in the main chain. The side chain may be formed from repeating units that are connected by para bonds, or it may have a portion that is partially connected by ortho bonds.

[0025] The following general formula (1) represents a continuous repeating unit formed by the aforementioned para-position bonding: (In the formula, R １ , R ２ Each is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may have substituents, and R ３ Each of these is a repeating unit represented by (which independently represents a hydrocarbon group having 1 to 10 carbon atoms, which may have substituents), and the rearrangement structure is represented by the following general formula (2): (In the formula, R １ , R ２ Each is independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may have substituents, and R ３ Each is independently a hydrocarbon group having 1 to 10 carbon atoms, which may have substituents, and R ３ ' is the aforementioned R ３ It is preferable to have a rearrangement structure represented by (representing a divalent group from which one hydrogen atom has been removed). The "~" in the general formula (2) indicates that the structure beyond it is not particularly limited. The "~" portion may be formed from phenylene ether units that are connected by para bonds, or it may have a portion that is partially connected by ortho bonds.

[0026] The aforementioned rearrangement structure is formed, for example, by a rearrangement reaction represented by the following equation, and is sometimes called a methylene bridge rearrangement.

[0027]

[0028] In the above general formulas (1) and (2), R １ , R ２ , R３ Examples of C1-C10 hydrocarbon groups in this context include C1-C10 alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, t-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, and decyl groups; C6-C10 aryl groups such as phenyl, 4-methylphenyl, 1-naphthyl, and 2-naphthyl groups; and C7-C10 aralkyl groups such as benzyl, 2-phenylethyl, and 1-phenylethyl groups.

[0029] If the hydrocarbon group has substituents, examples of substituents include halogen atoms such as fluorine atoms, and alkoxy groups such as methoxy groups. Specific examples of hydrocarbon groups with substituents include, for example, trifluoromethyl groups.

[0030] Among these, R １ , R ２ As for the hydrogen atom, a methyl group is preferred, and a hydrogen atom is more preferred, R ３ A methyl group is preferred as the component.

[0031] The aforementioned R ３’ is the aforementioned R ３ This represents a divalent group from which one hydrogen atom has been removed, and a methylene group is preferred.

[0032] Specific examples of the repeating unit of the general formula (1) include repeating units derived from 2,6-dimethyl-1,4-phenylene ether, 2,6-diethyl-1,4-phenylene ether, 2-methyl-6-ethyl-1,4-phenylene ether, and 2,6-dipropyl-1,4-phenylene ether. Among these, the repeating unit derived from 2,6-dimethyl-1,4-phenylene ether is preferred.

[0033] The PPE component having the aforementioned rearrangement structure is preferably a homopolymer having repeating units of general formula (1), or a copolymer containing two or more different repeating units of general formula (1) and having the rearrangement structure represented by general formula (2).

[0034] Furthermore, the PPE component having the rearrangement structure may contain repeating units other than those of general formula (1) as long as it does not impair the effects of the present invention. In that case, the copolymer containing the repeating units of general formula (1) and repeating units other than those of general formula (1) may have the rearrangement structure represented by general formula (2). The content of such repeating units other than those of general formula (1) is not particularly limited as long as it does not impair the effects of the present invention, but for example, it is preferably about 5 mol% or less in the copolymer, and more preferably it is not included at all.

[0035] The amount of the dislocation structure in the PPE component having the dislocation structure (hereinafter also referred to as "dislocation amount") is 3.0 mol% or more, preferably 3.5 mol% or more, and more preferably 3.7 mol% or more, relative to the total structural units constituting the PPE. Furthermore, the dislocation amount is preferably 15 mol% or less, more preferably 12 mol% or less, and even more preferably 10 mol% or less. When the dislocation amount in the PPE component having the dislocation structure is within the above range, the number of bent structures increases, the orientation and re-aggregation of polymer molecules after dissolution in the solvent is reduced, and the solubility in the solvent is improved.

[0036] The aforementioned dislocation structure is observed in the nuclear magnetic resonance spectrum ( １ In 1H-NMR measurements, it is preferable to show peaks in the ranges of 3.8–4.0 ppm and 6.8–7.0 ppm. Typically, PPE shows a peak around 6.4–6.6 ppm, which is a peak originating from the hydrogen atoms at positions 3 and 5 of the benzene ring in the PPE main chain. PPE having the rearrangement structure shows peaks in the ranges of 3.8–4.0 ppm and 6.8–7.0 ppm, in addition to the peak around 6.4–6.6 ppm. The chemical shift at 3.8–4.0 ppm is due to R in the rearrangement structure. ３’ This originates from the proton of the divalent group (e.g., methylene group) shown, and the chemical shift of 6.8 to 7.0 ppm is due to the R at the 3 and 5 positions of PPE in the rearrangement structure. １ , R ２ It originates from the protons of the group (for example, the hydrogen atoms at positions 3 and 5 of the benzene ring bonded to the ortho position via a methylene group).

[0037] The molecular weight of the PPE is not particularly limited, but it is preferably 40,000 to 100,000 in weight-average molecular weight (Mw), and more preferably 50,000 to 80,000. The number-average molecular weight (Mn) is preferably 7,000 to 30,000, and more preferably 8,000 to 20,000. The molecular weight dispersion (Mw / Mn) is preferably 3.5 to 8.0, and more preferably 4.0 to 6.0.

[0038] The PPE component content is preferably 95% by mass or more, more preferably 98% by mass or more, and even more preferably substantially composed of only PPE components (100% by mass) of the total components forming the PPE melt extruded molded article. Having the PPE component content in the PPE melt extruded molded article within the above range is preferable because it not only has excellent mechanical strength but also excellent heat resistance, chemical resistance, flame retardancy, etc.

[0039] The PPE component used in the present invention may include PPE that does not have a rearrangement structure. Examples of PPE that does not have a rearrangement structure include a homopolymer having repeating units of general formula (1), a copolymer containing two or more different repeating units of general formula (1), and a copolymer having repeating units of general formula (1) and repeating units other than general formula (1). The content of repeating units of general formula (1) or less in the copolymer can be as described above.

[0040] <Components other than PPE component> The PPE melt extruded molded article of the present invention may contain resin components other than the PPE component. Examples of resin components other than PPE component include styrene, polyethylene, polypropylene, polyamides such as polyamide 4, polyamide 6, polyamide 10, polyamide 11, polyamide 66, polyamide 6T, polyamide 6T / 11, polyesters such as polyethylene terephthalate and polybutylene terephthalate, and polycarbonates. However, the content of these components is preferably 5% by mass or less, more preferably 2% by mass or less, and even more preferably none (0% by mass).

[0041] Furthermore, the PPE melt-extruded molded article of the present invention may also contain additives such as lubricants, plasticizers, antioxidants, ultraviolet absorbers, dulling agents, and antistatic agents, to the extent that they do not impair the effects of the present invention.

[0042] <PPE molten extruded article> The PPE molten extruded article of the present invention can also be manufactured by the method for manufacturing a PPE molten extruded article described later.

[0043] The glass transition temperature of a PPE melt-extruded molded article is not particularly limited, but is preferably 205°C or higher, and more preferably 206°C or higher. A glass transition temperature within this range is preferable because it increases heat resistance. Furthermore, the upper limit of the glass transition temperature is not particularly limited, but is preferably 230°C or lower, and more preferably 220°C or lower.

[0044] The shape of the melt-extruded article is not particularly limited, and can be molded into various shapes such as pellets, films, sheets, plates, pipes, tubes, rods, fibers, nonwoven fabrics, paper, and cloth.

[0045] The PPE melt-extruded molded articles of the present invention exhibit excellent solubility in solvents and have a low amount of insoluble matter when dissolved in a solvent. Examples of soluble solvents include alcohol-based solvents such as methanol, ethanol, and isopropyl alcohol; acetic acid ester-based solvents such as methyl acetate, ethyl acetate, and butyl acetate; ketone-based solvents such as acetone and methyl ethyl ketone; aromatic solvents such as toluene; and cyclic ether-based solvents such as dioxane. The articles can be dissolved in any of these solvents individually, or in mixtures of two or more of these solvents.

[0046] Furthermore, the PPE melt extruded molded article of the present invention does not require a high temperature for dissolution in the above solvent, and can be dissolved at room temperature to about 60°C. Also, the solid content concentration of the PPE melt extruded molded article solution is not particularly limited and can be set appropriately depending on the intended use of the PPE, but the PPE melt extruded molded article solution of the present invention can have a solid content concentration of about 5 to 80% by mass.

[0047] 2. Method for manufacturing a PPE melt extruded article The method for manufacturing a PPE melt extruded article of the present invention comprises the step of melting and extruding PPE, which is the raw material, using an extruder equipped with a cylinder, a screw, and an extrusion nozzle, characterized in that the nozzle hole diameter of the extrusion nozzle is 2 mm or less.

[0048] Examples of PPE used as a raw material include homopolymers having the repeating unit of general formula (1), copolymers containing two or more different repeating units of general formula (1), and copolymers having the repeating unit of general formula (1) and repeating units other than general formula (1). The content of repeating units other than general formula (1) in the copolymer can be as described above. Among these, homopolymers having the repeating unit of general formula (1) are preferred.

[0049] Examples of homopolymers having the repeating unit of the general formula (1) include poly(2,6-dimethyl-1,4-phenylene ether), poly(2,6-diethyl-1,4-phenylene ether), poly(2-methyl-6-ethyl-1,4-phenylene ether), and poly(2,6-dipropyl-1,4-phenylene ether), but among these, poly(2,6-dimethyl-1,4-phenylene ether) is preferred.

[0050] Commercially available poly(2,6-dimethyl-1,4-phenylene ether) products can also be suitably used. Specifically, examples include PPO630, PPO640, and PPO646 from SABIC Innovative Plastics, PX100L and PX100F from Mitsubishi Engineering Plastics Corporation, and LXN035 and LXN040 from Bluestar.

[0051] The glass transition temperature of the PPE raw material is preferably 170°C or higher, more preferably 200°C or higher, and even more preferably 210°C or higher. Furthermore, while there is no particular upper limit to the glass transition temperature, it is preferably 230°C or lower. Having the glass transition temperature of the PPE raw material within this range is preferable because it allows for the production of a PPE melt-extruded molded article with high heat resistance.

[0052] Furthermore, the raw materials used in the present invention may include two or more types of PPE having different glass transition temperatures. Specifically, in addition to PPE with a glass transition temperature of 170°C or higher, PPE with a glass transition temperature of less than 170°C may be included. Adding PPE with a glass transition temperature of less than 170°C reduces the melt viscosity and improves fluidity, but tends to reduce the amount of dislocations in the PPE.

[0053] In the raw material PPE, the content of PPE having a glass transition temperature of 170°C or higher is preferably 80% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and it is particularly preferable that it consists only of PPE having a glass transition temperature of 170°C or higher. Furthermore, there is no particular upper limit to the content of PPE having a glass transition temperature of 170°C or higher, but it is preferably 100% by mass or less. In the present invention, including PPE with a high glass transition temperature (i.e., high molecular weight) within the above range is preferable because it results in excellent mechanical strength, heat resistance, chemical resistance, flame retardancy, etc., of the resulting PPE melt extruded molded article.

[0054] Furthermore, along with the raw material PPE, the product may also contain resin components and additives other than PPE. The resin components and additives other than PPE are as described above. The content of resin components other than PPE is preferably 5% by mass or less, more preferably 2% by mass or less, and even more preferably none (0% by mass).

[0055] As the extruder equipped with the cylinder, screw, and extrusion nozzle, a single-screw extruder or a twin-screw extruder, which are commonly used in this field, can be used. In the present invention, it is preferable to use a twin-screw extruder. The extruder is not limited to this, and any extruder that can effectively achieve the objective of shearing the polymer is acceptable.

[0056] The nozzle hole diameter of the extrusion nozzle is 2 mm or less, preferably 1.8 mm or less, and more preferably 1.5 mm or less. A nozzle hole diameter of 2 mm or less allows for faster cooling of the PPE molten extruded molded body, suppressing surface oxidation, and consequently reducing the amount of insoluble matter during solvent dissolution.

[0057] The peripheral speed of the screw is required to generate enough dislocation structures to dissolve in the solvent, and is preferably 10 m / min or more, more preferably 15 m / min or more, and more preferably 20 m / min or more. Furthermore, there is no particular upper limit to the peripheral speed of the screw, but it is preferably 94.2 m / min or less. In the present invention, by increasing the screw rotation speed to make the peripheral speed of the screw 10 m / min or more, it is possible to form PPE that satisfies the amount of dislocations necessary for dissolution in the solvent.

[0058] The shape of the screw is not particularly limited; it should be one that can apply a shear force sufficient to cause a rearrangement reaction in the raw material, PPE.

[0059] The temperature inside the cylinder (extrusion temperature) is 260°C or higher, preferably 280°C or higher, and more preferably 300°C or higher. Furthermore, the extrusion temperature is preferably 350°C or lower, and more preferably 345°C or lower. By setting the temperature inside the cylinder within the above range, it is possible to form PPE that satisfies the amount of dislocations necessary for dissolution in the solvent, and surface oxidation of the PPE molten extruded molded article can be suppressed. As a result, the amount of insoluble matter during solvent dissolution can be suppressed, which is preferable.

[0060] An example of manufacturing PPE molten extruded products (pellets) will be explained using Figure 1. PPE, the raw material, is fed from the hopper 1 in Figure 1 into an extruder 2 equipped with a cylinder, screw, and extrusion nozzle 5. The molten PPE is discharged from the nozzle, cooled on an air-cooled belt conveyor 3, and pelletized by a pelletizer 4. The extruder 2 may also be equipped with a degassing vent 10. To prevent oxygen from entering the extruder 2, an inert gas may be introduced beyond the degassing vent 10, or a vacuum pump may be attached.

[0061] The discharge rate from nozzle 5 is preferably 5 g / min or more, more preferably 10 g / min or more, and even more preferably 15 g / min or more. Furthermore, there is no particular upper limit to the discharge rate, but it is preferably 50,000 g / min or less, more preferably 40,000 g / min or less, and even more preferably 30,000 g / min or less.

[0062] The resulting PPE melt-extruded molded product has good solubility in solvents and a low amount of insoluble matter when dissolved in solvents, so it can be used in various applications such as wiring board materials, wire insulation materials, coatings for lithium-ion battery packages, motor coil wire insulation materials, heat-resistant paints, can interior coatings, film capacitors, and insulating paper.

[0063] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. The evaluation methods for physical properties, etc. in the following examples are as follows, and unless otherwise specified, the measurement of physical properties, etc. means measurement at room temperature (20-25°C) / relative humidity 40-50%.

[0064] (1) Glass transition temperature (Tg) Using a differential scanning calorimetry analyzer (model: DSC-Q100) manufactured by TA Instruments Inc., 2 mg of the obtained PPE pellet was measured in a nitrogen atmosphere from 30°C to 250°C at a heating rate of 10°C / min. The temperature at the intersection of the extension of the baseline below the glass transition temperature and the tangent line showing the maximum slope in the transition region was defined as the glass transition temperature (Tg).

[0065] (2) Amount of insoluble matter: Dissolve the polyphenylene ether molten extruded molded body in toluene at 40°C to prepare a solution with a solid content of 10% by mass, and let it stand for 6 hours. Then, filter the solution and measure the amount of insoluble matter (Ag) that did not dissolve in toluene. Calculate the amount of insoluble matter using the following formula: Amount of insoluble matter (mass%) = (A / Amount of polyphenylene ether molten extruded molded body used (g)) × 100

[0066] (3) The amount of dislocation structure in PPE at a resonance frequency of 600 MHz １The measurement was performed using 1H-NMR. A BRUKER NMR spectrometer (model name: AVANCE-NEO600) was used, and the measurement was performed as follows: 10 mg of PPE pellets obtained in the examples and comparative examples were dissolved in deuterated chloroform, and the solution was filled into an NMR tube within 2 hours for measurement. Deuterated chloroform was used as the locking solvent, with a waiting time of 1 second, a data acquisition time of 4 seconds, and 64 integration cycles. Deuterated benzene may also be used as the solvent. The rearrangement structure amount was analyzed as follows: R at positions 3 and 5 of PPE. １ , R ２ Peaks originating from the proton of the base and R in the dislocation structure ３’ The peak integrals of the divalent groups (such as methylene groups) shown are denoted as A and B, and the rearrangement structure weight was calculated using the following formula: Rearrangement structure weight (mol%) = (B / (A + B)) × 100

[0067] (4) Absorbance-to-Height Ratio (C / B) PPE pellets obtained in the examples and comparative examples were used as measurement samples. An infrared spectrophotometer (FTIR) (product name: 3100FT-IR / 600UMA, Varian Corporation) was used to measure the absorbance of the obtained samples by microtransmission under the following conditions. (Measurement conditions) Field of view: 80 μm × 80 μm Measurement wavelength range: 400 cm －１ From 4000cm －１ Number of integration: 128 times Resolution: 4cm －１ The obtained spectrum, wavelength 1550–1480 cm －１ The minimum value and 1900-1800 cm －１ A baseline was drawn connecting the minimum values, and the evaluation was performed using the peak height (peak absorbance height) from this baseline. (1610–1590 cm) －１ The peak height is 1600 cm －１ Absorbance height (B), 1660–1640 cm －１ The peak height is 1650 cm. －１ The absorbance height (C) was defined as the C / B ratio.

[0068] (5) Peripheral speed of the screw The peripheral speed of the screw was determined by the following formula: Peripheral speed of the screw (m / min) = Screw diameter (mm) × 0.00314 × Screw rotation speed (rpm)

[0069] Example 1 Poly(2,6-dimethyl-1,4-phenylene ether) (PPO (trademark registered) 640, glass transition temperature (Tg): 221°C, manufactured by SABIC Innovative Plastic) was extruded using a twin-screw extruder manufactured by Technovel Co., Ltd. (product name: KZW15TW-30MG). The twin-screw extruder has four cylinder zones, and the cylinders from the hopper side were designated as cylinder 1, 2, 3, and 4. Cylinder 1 was set to 280°C, cylinders 2-4 and the cylinder head were set to 330°C, and the screw rotation speed was set to 700 rpm, resulting in a screw peripheral speed of 33.0 m / min. The discharge rate was 50 g / min. A vent was attached to cylinder 3, and the vent was evacuated.

[0070] A nozzle with a diameter of φ0.8 mm was attached downstream of the extruder, and the extruded resin was dropped onto a metal conveyor, picked up at 100 m / min, cut with a strand cutter, and obtained pellets. The physical properties of the obtained pellets are shown in Table 1.

[0071] Based on the measurement method for "(3) Amount of dislocation structure in PPE" of the obtained PPE pellets, １ 1H-NMR measurements were performed. As a result, when deuterated chloroform was used at 7.28 ppm, peaks were observed around 6.9 ppm, 6.48 ppm, and 3.87 ppm. The peak around 6.9 ppm corresponds to the protons at positions 3 and 5 of PPE generated by the rearrangement (i.e., in the rearrangement structure), the peak around 6.48 ppm corresponds to the protons at positions 3 and 5 of PPE in the main chain, and the peak around 3.87 ppm corresponds to the methylene group in the methylene bridge generated by the rearrangement.

[0072] Examples 2-6 and Comparative Examples 1-3: Pellets were obtained in the same manner as in Example 1, except that the screw rotation speed, screw peripheral speed, extrusion temperature, and nozzle hole diameter were changed as shown in Table 1. The physical properties of the obtained pellets are shown in Table 1. In Table 1, "PX100L" is poly(2,6-dimethyl-1,4-phenylene ether) (PX100L, glass transition temperature (Tg): 210°C, manufactured by Mitsubishi Engineering Plastics Corporation).

[0073]

[0074] As shown in Table 1, the PPE pellets obtained in the examples of the present invention had a low amount of insoluble matter when dissolved in toluene and exhibited excellent solvent solubility. On the other hand, the PPE pellets of the comparative examples had a high amount of insoluble matter when dissolved in toluene and exhibited poor solvent solubility.

[0075] 1. Hopper 2. Extruder 3. Air-cooled belt conveyor 4. Pelletizer 5. Extrusion nozzle 10. Vent for degassing

Claims

1. A polyphenylene ether melt extruded molded article containing a polyphenylene ether component, wherein the polyphenylene ether component is a polyphenylene ether component having a rearrangement structure in which ortho bonds are connected within repeating units that are continuous by para bonds, the amount of the rearrangement structure is 3.0 mol% or more relative to the total polyphenylene ether structural units in the polyphenylene ether component, and measured by infrared spectroscopy, the wavenumber is 1600 cm², which is derived from skeletal vibrations due to expansion and contraction between carbon atoms of the benzene ring. －１ Absorbance height B and C = O, derived from stretching vibration, wavenumber 1650 cm² －１ A polyphenylene ether melt extruded article characterized in that the ratio of absorbance height C to absorbance height B (C / B) is 0.04 or less.

2. The polyphenylene ether molten extruded molded body according to claim 1, characterized in that the amount of insoluble matter when the polyphenylene ether molten extruded molded body is dissolved in toluene under the following conditions is 15% by mass or less. (Method for measuring the amount of insoluble matter) The polyphenylene ether molten extruded molded body is dissolved in toluene at 40°C to prepare a solution with a solid content concentration of 10% by mass, and left to stand for 6 hours. Then, the solution is filtered and the amount of insoluble matter (Ag) that did not dissolve in toluene is measured. The amount of insoluble matter is calculated using the following formula: Amount of insoluble matter (mass%) = (A / Amount of polyphenylene ether molten extruded molded body used (g)) × 100 3. The polyphenylene ether melt extruded article according to claim 1, characterized in that the polyphenylene ether component content is 95% by mass or more of the total components forming the polyphenylene ether melt extruded article.

4. The repeating units that are continuous due to the para-position bonds are represented by the following general formula (1): (In the formula, R １ , R ２ are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms that may have a substituent, and R ３ are each independently a hydrocarbon group having 1 to 10 carbon atoms that may have a substituent), and the rearrangement structure is represented by the following general formula (2): (In the formula, R １ , R ２ are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms that may have a substituent, and R ３ are each independently a hydrocarbon group having 1 to 10 carbon atoms that may have a substituent, and R ３ ' represents a divalent group obtained by removing one hydrogen atom from the above R ３ ), and the polyphenylene ether melt-extruded molded body according to claim 1, characterized in that it has the structure represented by the above formula.

5. The polyphenylene ether melt extruded molded article according to claim 1, characterized in that the polyphenylene ether melt extruded molded article is a polyphenylene ether pellet.

6. A method for producing a polyphenylene ether molten extruded molded article according to any one of claims 1 to 5, comprising the step of melting and extruding polyphenylene ether, which is a raw material, using an extruder equipped with a cylinder, a screw, and an extrusion nozzle, characterized in that the nozzle hole diameter of the extrusion nozzle is 2 mm or less.

7. A method for producing a polyphenylene ether melt-extruded molded article according to claim 6, characterized by melt-extrusion at an extrusion temperature of 350°C or lower.

8. The method for producing a polyphenylene ether melt extruded article according to claim 6, characterized in that the peripheral speed of the screw is 10 m / min or more.

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