All-aromatic ether ketone resin compositions and their molded articles, as well as phosphorus stabilizers

Abstract

A fully aromatic ether ketone resin composition comprising (A) a fully aromatic ether ketone resin and (B) a phosphorus-based stabilizer, wherein the (B) phosphorus-based stabilizer contains (B1) a dihydrogen phosphate and (B2) a hydrogen phosphate, wherein (B1) the dihydrogen phosphate is one or more of an alkali metal dihydrogen phosphate or one or more of an alkaline earth metal dihydrogen phosphate, and (B2) the hydrogen phosphate is one or more of an alkali metal hydrogen phosphate or one or more of an alkaline earth metal hydrogen phosphate, and (B1) the dihydrogen phosphate and (B2) the hydrogen phosphate are contained in a predetermined combination, and the total content of the (B) phosphorus-based stabilizer is 100 to 5000 ppm by mass.

Description

Technical Field

[0001] This invention relates to a fully aromatic ether ketone resin composition and its molded articles, as well as a phosphorus-based stabilizer. Prior Technology

[0002] All-aromatic ether ketone resins are also simply referred to as PAEK (polyaryletherketone), and products such as PEEK (polyetheretherketone), PEK (polyetherketone), PEKK (polyetherketoneketone), and PAKEKK (polyetherketoneetherketoneketone) are already available on the market. Since all-aromatic ether ketone resins generally have high melting points (above 300°C), they must be heated to high temperatures to melt. However, at such high temperatures, there is a lack of stability against thermal degradation. Therefore, various countermeasures have been proposed to achieve stabilization in the molten state (see Patent Documents 1 and 2). The resin compositions described in Patent Documents 1 and 2 achieve stabilization against thermal oxidation in the molten state by adding phosphates or mixtures of phosphates. [Previous Technical Documents] [Patent Literature]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2018-520257 [Patent Document 2] Japanese Patent Application Publication No. 2018-520258 Summary of the Invention

[0004] [The problem the invention aims to solve]

[0005] On the other hand, it is known that the viscosity of fully aromatic ether ketone resins increases with residence time in the molten state. This viscosity increase is generally attributed to crosslinking caused by oxidation at very high processing temperatures (greater than 350°C) associated with the resin. The resin compositions described in Patent Documents 1 and 2 aim to stabilize the molten state against thermal oxidation. However, the increase or decrease in viscosity with residence time is influenced by many factors, such as chain elongation due to reactions between residual reactive ends, oxidative crosslinking, and side reactions caused by residual catalysts, as well as chain breakage due to heat, oxygen, and residual impurities. Therefore, simply stabilizing the molten viscosity against thermal oxidation is insufficient to improve the residence stability of the molten viscosity.

[0006] Furthermore, according to the inventors' research, phosphates (dihydrogen phosphates (NaH₂PO₄, etc.), or mixtures of dihydrogen phosphates and hydrogen phosphates (Na₂HPO₄, etc.)) are highly corrosive to metals, especially in the presence of water and at high temperatures. Therefore, as described above, when phosphates are used to stabilize thermal oxidation in the molten state, metal parts in equipment such as extruders may corrode, potentially leading to manufacturability deterioration.

[0007] The present invention was made in view of the aforementioned problems of the prior art, and its object is to provide a fully aromatic ether ketone resin composition and its molded articles with excellent retention stability of melt viscosity and manufacturability, as well as a phosphorus-based stabilizer with excellent resistance to metal corrosion at high temperatures. [Methods used to solve problems]

[0008] To address the aforementioned problems, the inventors conducted in-depth research and discovered that adjusting the pH value of the all-aromatic ether ketone resin composition to a predetermined range (neutral region) can improve the retention stability of the melt viscosity. Furthermore, the inventors also discovered that using specific phosphates in a specific combination can improve resistance to metal corrosion at high temperatures, thus completing this invention.

[0009] One aspect of the present invention that solves the above problems is described below. (1) A fully aromatic ether ketone resin composition comprising (A) a fully aromatic ether ketone resin and (B) a phosphorus-based stabilizer, wherein The aforementioned phosphorus-based stabilizer (B) contains (B1) dihydrogen phosphate and (B2) hydrogen phosphate. The above-mentioned (B1) dihydrogen phosphate is one or more alkali metal dihydrogen phosphates, or one or more dihydrogen phosphates of metals selected from the group consisting of alkaline earth metals and magnesium. The above-mentioned (B2) hydrogen phosphate is one or more alkali metal hydrogen phosphates, or one or more hydrogen phosphates of metals selected from the group consisting of alkaline earth metals and magnesium. When the above-mentioned (B1) dihydrogen phosphate is one or more alkali metal dihydrogen phosphates, the above-mentioned (B2) hydrogen phosphate is one or more hydrogen phosphates of a metal selected from the group consisting of alkaline earth metals and magnesium. When the above-mentioned (B1) dihydrogen phosphate is one or more dihydrogen phosphates selected from the group consisting of alkaline earth metals and magnesium, the above-mentioned (B2) hydrogen phosphate is one or more hydrogen phosphates of an alkali metal. The total content of the phosphorus stabilizers (B) mentioned above is 100~5000 ppm by mass.

[0010] (2) The fully aromatic ether ketone resin composition as described in (1) above, wherein, in the phosphorus stabilizer of (B) above, when the mole number of the alkali metal is set to [MI], the mole number of the metal selected from the group consisting of alkaline earth metals and magnesium is set to [MI II], and the mole number of phosphorus is set to [P], 1.00 < ([MI] + [MI II] × 2) / [P] < 2.00.

[0011] (3) The fully aromatic ether ketone resin composition as described in (1) or (2) above, wherein, in the phosphorus stabilizer of (B) above, when the mole number of the alkali metal is set to [MI], the mole number of the metal selected from the group consisting of alkaline earth metals and magnesium is set to [MI II], and the mole number of phosphorus is set to [P], the following condition is satisfied: 1.10≤([MI]+[MI II]×2) / [P]≤1.80.

[0012] (4) The fully aromatic ether ketone resin composition described in any one of (1) to (3) above, wherein the fully aromatic ether ketone resin of (A) above is selected from one or more of the group consisting of polyether ketone, polyether ether ketone and polyether ketone ether ketone.

[0013] (5) The all-aromatic ether ketone resin composition described in any one of (1) to (4) above, wherein the (B1) dihydrogen phosphate is a dihydrogen phosphate of one or more metals selected from the group consisting of sodium, potassium, magnesium and calcium. The above-mentioned (B2) hydrogen phosphate is a hydrogen phosphate of one or more metals selected from the group consisting of sodium, potassium, magnesium and calcium.

[0014] (6) The fully aromatic ether ketone resin composition described in any one of (1) to (5) above, wherein the total content of the phosphorus stabilizer in (B) above is 100 to 1000 ppm by mass.

[0015] (7) The fully aromatic ether ketone resin composition described in any one of (1) to (6) above, wherein the fully aromatic ether ketone resin of (A) above is a polyether ketone.

[0016] (8) A molded article which is formed from the fully aromatic ether ketone resin composition described in any one of (1) to (7) above.

[0017] (9) A phosphorus-based stabilizer containing (B1) dihydrogen phosphate and (B2) hydrogen phosphate. The above-mentioned (B1) dihydrogen phosphate is one or more alkali metal dihydrogen phosphates, or one or more dihydrogen phosphates of metals selected from the group consisting of alkaline earth metals and magnesium. The above-mentioned (B2) hydrogen phosphate is one or more alkali metal hydrogen phosphates, or one or more hydrogen phosphates of metals selected from the group consisting of alkaline earth metals and magnesium. When the above-mentioned (B1) dihydrogen phosphate is one or more alkali metal dihydrogen phosphates, the above-mentioned (B2) hydrogen phosphate is one or more hydrogen phosphates of a metal selected from the group consisting of alkaline earth metals and magnesium. When the above-mentioned (B1) dihydrogen phosphate is one or more dihydrogen phosphates of a metal selected from the group consisting of alkaline earth metals and magnesium, the above-mentioned (B2) hydrogen phosphate is one or more hydrogen phosphates of an alkali metal.

[0018] (10) The phosphorus stabilizer described in (9) above, wherein when the mole number of the alkali metal is set to [MI], the mole number of the metal selected from the group consisting of alkaline earth metals and magnesium is set to [MI II], and the mole number of phosphorus is set to [P], 1.00 < ([MI] + [MI II] × 2) / [P] < 2.00.

[0019] (11) The phosphorus stabilizer as described in (9) or (10) above, wherein the (B1) dihydrogen phosphate is a dihydrogen phosphate of one or more metals selected from the group consisting of sodium, potassium, magnesium and calcium. The above-mentioned (B2) hydrogen phosphate is a hydrogen phosphate of one or more metals selected from the group consisting of sodium, potassium, magnesium and calcium.

[0020] (12) The phosphorus stabilizer described in any of (9) to (11) above, wherein when the mole number of the alkali metal is set as [MI], the mole number of the metal selected from the group consisting of alkaline earth metals and magnesium is set as [MI II], and the mole number of phosphorus is set as [P], the following condition is satisfied: 1.10≤([MI]+[MI II]×2) / [P]≤1.80. [Invention Benefits]

[0021] According to the present invention, a fully aromatic ether ketone resin composition and its molded articles are provided, which have excellent retention stability of melt viscosity and manufacturability, as well as a phosphorus-based stabilizer with low metal corrosion at high temperatures. Simple Explanation of the Diagram

[0022] [Figure 1] is a graph showing the relationship between pH and the ion ratio of phosphate ([Na+] / [P]). Implementation

[0023] [The form in which the invention is carried out]

[0024] <Fully Aromatic Ether-Ketone Resin Composition> The fully aromatic ether ketone resin composition of this embodiment (hereinafter also referred to as the "resin composition") comprises (A) a fully aromatic ether ketone resin and (B) a phosphorus-based stabilizer. Furthermore, the phosphorus-based stabilizer (B) comprises (B1) a dihydrogen phosphate and (B2) a hydrogen phosphate. Then, (B1) the dihydrogen phosphate is one or more alkali metal dihydrogen phosphates, or one or more dihydrogen phosphates selected from the group consisting of alkaline earth metals and magnesium. Furthermore, (B2) the hydrogen phosphate is one or more alkali metal hydrogen phosphates, or one or more hydrogen phosphates selected from the group consisting of alkaline earth metals and magnesium. Moreover, when (B1) the dihydrogen phosphate is one or more alkali metal dihydrogen phosphates, (B2) the hydrogen phosphate is one or more hydrogen phosphates selected from the group consisting of alkaline earth metals and magnesium. Furthermore, when (B1) dihydrogen phosphate is one or more dihydrogen phosphates selected from the group consisting of alkaline earth metals and magnesium, (B2) hydrogen phosphate is one or more hydrogen phosphates of an alkali metal. Moreover, the total content of (B) phosphorus-based stabilizers is 100 to 5000 ppm by mass. Furthermore, in the following description, metals selected from the group consisting of alkaline earth metals and magnesium are referred to as "alkaline earth metals, etc."

[0025] The fully aromatic ether ketone resin composition of this embodiment improves the retention stability of melt viscosity by adjusting the pH to the neutral range using (B1) dihydrogen phosphate and (B2) hydrogen phosphate. The reaction mechanism is speculated as follows. As a polymerization method for fully aromatic ether ketone resins, two types can be listed: (1) nucleophilic aromatic substitution reaction and (2) Friedel-Crafts acylation reaction. In this embodiment, the polymerized product is taken as the product polymerized by (1) nucleophilic aromatic substitution reaction. That is, any of the polyetherketone, polyetheretherketone, and polyetherketone etherketone ketone that are (A) fully aromatic ether ketone resins are polymerized by (1) nucleophilic aromatic substitution reaction. The fully aromatic ether ketone resin polymerized by (1) nucleophilic aromatic substitution reaction is polymerized under high temperature (above 300°C) and alkaline conditions with phenolic hydroxyl groups and aromatic halogens as reactive groups. In order to stop the polymerization, a method is generally adopted to break the end equilibrium by end-capping reaction and stop the polymerization (Japanese Patent Application Publication No. 61-138626). The alkali metal salt used as an alkaline catalyst is removed by a washing step with water after polymerization. From the perspective of polymerization mechanism, if the end-capping reaction rate is low, coupled with conditions such as residual alkaline catalyst, polymerization will occur between reactive ends during melt retention, resulting in increased molecular weight and viscosity. Therefore, in this embodiment, by setting the pH of the resin composition to the neutral range, the reaction caused by the functional groups at the ends after polymerization can be suppressed, thereby improving the retention stability of melt viscosity.

[0026] On the other hand, in the resin composition of this embodiment, (B1) dihydrogen phosphate is one or more alkali metal dihydrogen phosphates or one or more alkaline earth metal dihydrogen phosphates. Furthermore, (B2) hydrogen phosphate is one or more alkali metal hydrogen phosphates or one or more alkaline earth metal hydrogen phosphates. Moreover, this embodiment is characterized by combining (B1) dihydrogen phosphate and (B2) hydrogen phosphate. That is, when (B1) dihydrogen phosphate is an alkali metal dihydrogen phosphate, (B2) hydrogen phosphate is an alkaline earth metal hydrogen phosphate. Conversely, when (B1) dihydrogen phosphate is one or more alkaline earth metal dihydrogen phosphates, (B2) hydrogen phosphate is one or more alkali metal hydrogen phosphates. In other words, (B1) dihydrogen phosphate and (B2) hydrogen phosphate are not both simultaneously alkali metal salts or alkaline earth metal salts; rather, when one is an alkali metal salt, the other is an alkaline earth metal salt. In this embodiment, by combining (B1) dihydrogen phosphate and (B2) hydrogen phosphate as described above, metal corrosion can be suppressed. The reaction mechanism is presumed to be as follows: Alkali metal phosphates are generally soluble in water, but if metal ions with a valence of divalent or higher (in this embodiment, ions of alkaline earth metals, etc.) are present, salts represented by M(I)M(II)PO4 will be formed. Furthermore, most of these salts are sparingly soluble (Metal Surface Technology, Vol. 28, No. 1, 1977). Therefore, it is inferred that the solubility of phosphates changes, acid formation is suppressed, and metal corrosivity is reduced. The components of the fully aromatic ether ketone resin composition of this embodiment will be described in detail below.

[0027] [(A) All-aromatic ether ketone resin] The fully aromatic resin composition of this embodiment, as (A) a fully aromatic ether ketone resin, includes one or more from the group consisting of polyether ketone (PEK), polyether ether ketone (PEEK), and polyether ketone ether ketone (PEKEKK). These fully aromatic ether ketone resins are alkaline because they are polymerized via (1) a nucleophilic aromatic substitution reaction. From this viewpoint, the pH of the fully aromatic ether ketone resin itself is preferably 9 to 12. Polyether ketone (PEK) is preferred as (A) the fully aromatic ether ketone resin.

[0028] As described above, two types of polymerization methods for fully aromatic ether ketone resins can be listed: (1) nucleophilic aromatic substitution reaction and (2) Fridell-Quaftylation reaction. Among the specific examples above, only polyether ketone ketone (PEKK) is polymerized by (2) Fridell-Quaftylation reaction. Such polyether ketone ketone (PEKK) is neutral.

[0029] [(B) Phosphorus-based stabilizers] In this embodiment, as described above, (B) the phosphorus-based stabilizer contains (B1) dihydrogen phosphate and (B2) hydrogen phosphate. Hereinafter, (B1) dihydrogen phosphate and (B2) hydrogen phosphate will be described separately.

[0030] ((B1) dihydrogen phosphate) The (B1) dihydrogen phosphate used in this embodiment is one or more alkali metal dihydrogen phosphates or one or more alkaline earth metal dihydrogen phosphates.

[0031] Examples of alkali metal dihydrogen phosphates include potassium dihydrogen phosphate, sodium dihydrogen phosphate, lithium dihydrogen phosphate, rubidium dihydrogen phosphate, and cesium dihydrogen phosphate. Furthermore, examples of dihydrogen phosphates, such as those of alkaline earth metals, include magnesium dihydrogen phosphate, calcium dihydrogen phosphate, strontium dihydrogen phosphate, and barium dihydrogen phosphate.

[0032] Among them, (B1) dihydrogen phosphate is preferably a dihydrogen phosphate of one or more metals selected from the group consisting of sodium, potassium, magnesium and calcium.

[0033] ((B2) hydrogen phosphate) The (B2) hydrogen phosphate used in this embodiment is one or more hydrogen phosphates of alkali metals or alkaline earth metals.

[0034] Examples of alkali metal hydrogen phosphates include dipotassium hydrogen phosphate, disodium hydrogen phosphate, dilithium hydrogen phosphate, dirubidium hydrogen phosphate, and dicesium hydrogen phosphate. Examples of hydrogen phosphates that are alkaline earth metals include magnesium hydrogen phosphate, calcium hydrogen phosphate, and barium hydrogen phosphate.

[0035] Among them, (B2) hydrogen phosphate is preferably selected from one or more metal hydrogen phosphates in the group consisting of sodium, potassium, magnesium and calcium.

[0036] In the phosphorus-based stabilizer of this embodiment (B), the combination of (B1) dihydrogen phosphate and (B2) hydrogen phosphate can be listed, for example, the following combinations, but this embodiment is not limited to the following combinations. (B1) Dihydrogen phosphate is potassium dihydrogen phosphate, while (B2) hydrogen phosphate is a combination of magnesium hydrogen phosphate. (B1) Dihydrogen phosphate is sodium dihydrogen phosphate, while (B2) hydrogen phosphate is a combination of calcium hydrogen phosphate. (B1) dihydrogen phosphate is magnesium dihydrogen phosphate, while (B2) hydrogen phosphate is a combination of dipotassium hydrogen phosphate. (B1) Dihydrogen phosphate is calcium dihydrogen phosphate, while (B2) hydrogen phosphate is a combination of disodium hydrogen phosphate. (B1) Dihydrogen phosphate is potassium dihydrogen phosphate, while (B2) hydrogen phosphate is a combination of magnesium hydrogen phosphate and calcium hydrogen phosphate. (B1) Dihydrogen phosphate is potassium dihydrogen phosphate and sodium dihydrogen phosphate, while (B2) hydrogen phosphate is a combination of magnesium hydrogen phosphate. (B1) Dihydrogen phosphate is potassium dihydrogen phosphate and sodium dihydrogen phosphate, while (B2) hydrogen phosphate is a combination of magnesium hydrogen phosphate and calcium hydrogen phosphate. (B1) Dihydrogen phosphate is magnesium dihydrogen phosphate and magnesium dihydrogen phosphate, while (B2) hydrogen phosphate is a combination of dipotassium hydrogen phosphate and disodium hydrogen phosphate.

[0037] In (B) phosphorus-based stabilizers, when the mole number of alkali metals is set as [MI], the mole number of alkaline earth metals, etc., is set as [MI II], and the mole number of phosphorus is set as [P], it is preferable to satisfy 1.00 < ([MI] + [MI II] × 2) / [P] < 2.00. This inequality will be explained with reference to FIG1. ​​Furthermore, since the mole number of [H₂PO₄] or [HPO₄] is equal to the mole number of phosphorus, they are both expressed as the mole number of phosphorus [P] in the above inequality. [Figure 1] shows the relationship between pH and the ion ratio of phosphate ([Na+] / [P]). In Figure 1, a [Na+] / [P] value of 1.00 indicates the composition of NaH2PO4, while a [Na+] / [P] value of 2.00 indicates the composition of Na2HPO4. Furthermore, when the [Na+] / [P] value is greater than 1.00 and less than 2.00, it represents a mixture of NaH2PO4 and Na2HPO4 compositions. In this state, the pH becomes neutral, and the retention stability of the melt viscosity increases.

[0038] In this embodiment, considering the presence of (B1) dihydrogen phosphate and (B2) hydrogen phosphate, and the valence of alkali metals (monovalent) and alkaline earth metals (divalent), the pH is in the neutral range when 1.00 < ([MI] + [MI II] × 2) / [P] < 2.00, thus improving the retention stability of the melt viscosity. Furthermore, it is preferable to satisfy 1.10 ≤ ([MI] + [MI II] × 2) / [P] ≤ 1.80.

[0039] The total content of the phosphorus-based stabilizer (B) above is 100~5000 ppm by mass. If it is less than 100 ppm by mass, the retention stability of the melt viscosity is poor; if it exceeds 5000 ppm by mass, the manufacturability is poor. This content is preferably 100~1000 ppm by mass, and even better if it is 200~800 ppm by mass.

[0040] [Other ingredients] In this embodiment, one or more common additives used in thermoplastic resins may be added as needed, such as lubricants, release agents, antistatic agents, surfactants, flame retardants, or organic polymer materials, inorganic or organic powder or flake fillers, etc. However, even when other components are added, the pH value of the resin composition must be within the neutral range.

[0041] To further improve resistance to metal corrosion, the resin composition of this embodiment is preferably free of water.

[0042] <Molded Products> The molded article of this embodiment is formed by molding the fully aromatic ether ketone resin composition of this embodiment described above. Because this resin composition exhibits excellent retention stability of melt viscosity, it can be stably used in molding processes involving prolonged exposure to high temperatures, such as injection molding for extended periods and long-term residence-based hardening extrusion. Furthermore, due to the excellent manufacturability of this resin composition, corrosion of the manufacturing equipment is minimal during the molding of the molded article.

[0043] There are no particular limitations on the method for manufacturing molded articles using the fully aromatic ether ketone resin composition of this embodiment, and known methods can be used. For example, the fully aromatic ether ketone resin composition of this embodiment can be fed into an extruder for melt mixing and pelletizing, and the pellets can be fed into an injection molding machine equipped with a predetermined mold for injection molding, thereby manufacturing the product.

[0044] As a molded product of this embodiment, it can be appropriately used in automobiles, aviation, heavy industry (steel, power plants), electronic components, and other applications.

[0045] <Phosphorus-based stabilizers> The phosphorus-based stabilizer of this embodiment contains (B1) dihydrogen phosphate and (B2) hydrogen phosphate. Furthermore, (B1) dihydrogen phosphate is one or more alkali metal dihydrogen phosphates, or one or more dihydrogen phosphates selected from the group consisting of alkaline earth metals and magnesium. Additionally, (B2) hydrogen phosphate is one or more alkali metal hydrogen phosphates, or one or more hydrogen phosphates selected from the group consisting of alkaline earth metals and magnesium. Then, when (B1) dihydrogen phosphate is one or more alkali metal dihydrogen phosphates, (B2) hydrogen phosphate is one or more hydrogen phosphates selected from the group consisting of alkaline earth metals and magnesium. When (B1) dihydrogen phosphate is one or more dihydrogen phosphates selected from the group consisting of alkaline earth metals and magnesium, the aforementioned (B2) hydrogen phosphate is one or more alkali metal hydrogen phosphates.

[0046] The phosphorus stabilizer of this embodiment is (B) phosphorus stabilizer included in the above-described aromatic ether ketone resin composition. Therefore, when added to the aromatic ether ketone resin composition, it exhibits excellent retention stability of melt viscosity. Furthermore, since the phosphorus stabilizer of this embodiment has very low metal corrosivity at high temperatures, when added to the aromatic ether ketone resin composition, for example, during extrusion using an extruder, it can prevent corrosion of metal parts inside the extruder.

[0047] As described above, the phosphorus stabilizer of this embodiment is (B) phosphorus stabilizer included in the all-aromatic ether ketone resin composition of this embodiment, and the existing description of (B) phosphorus stabilizer is applicable. The preferred embodiments and specific examples described in the description paragraph of (B) phosphorus stabilizer are also the same. Therefore, the detailed description of the phosphorus stabilizer of this embodiment is omitted.

[0048] To further improve resistance to metal corrosion, the phosphorus-based stabilizer in this embodiment is preferably free of water. [Example]

[0049] The present embodiment will be described in more detail below by way of examples, but the present embodiment is not limited to the following examples.

[0050] [Examples 1-6, Comparative Examples 1-7] ~Phosphorus-based stabilizers~ In the various embodiments, comparative examples, and reference examples, the (B1) dihydrogen phosphate and (B2) hydrogen phosphate shown in Tables 1 and 2 were mixed in the proportions shown in Tables 1 and 2 to obtain a phosphorus-based stabilizer. Furthermore, when the mole number of the alkali metal is set as [MI], the mole number of the alkaline earth metal is set as [MI II], and the mole number of phosphorus is set as [P], the values ​​calculated by the formula ([MI] + [MI II] × 2) / [P] are shown in Tables 1 and 2.

[0051] [evaluate] Accelerated tests were conducted according to the following steps to evaluate the metal corrosion resistance of the phosphorus stabilizers obtained in the various examples, comparative examples, and reference examples. (a) The phosphorus stabilizer used in the experiment was dried in an air dryer set at 180°C for 2 hours. (b) Weigh the dried phosphorus stabilizer into a mortar, with the same composition as the phosphate composition of each example, comparative example and reference example, so that the total amount of phosphate is 15 g, add 1.5 g of distilled water and mix. (c) The phosphate prepared in step (b) and a 15 mm × 15 mm × 3 mm metal test piece (steel type: Sanyo Special Steel Co., Ltd. SPM30) are placed in a pressure vessel with a PTFE inner cylinder and then treated at 200°C for 72 hours. (d) Using a cutting tool or similar tool, remove the phosphate and corrosion from the treated metal test piece and confirm the weight reduction after the test. The results are shown in Table 1. Furthermore, a weight reduction of less than 4% is rated as "good," while a reduction of more than 4% is rated as "poor." The evaluation results are shown in Tables 1 and 2.

[0052] [Table 1]

[0053] [Table 2]

[0054] As shown in Tables 1 and 2, Examples 1-7 all obtained good results in the evaluation of metal corrosion resistance, while Comparative Examples 1-7 all yielded poor results. That is, it can be seen that using (B1) dihydrogen phosphate and (B2) hydrogen phosphate in a predetermined combination, and including a phosphorus stabilizer at a predetermined content relative to the total, can improve metal corrosion resistance at high temperatures. Furthermore, Reference Example 1 is an example of adding disodium hydrogen phosphate as (B2) hydrogen phosphate alone; when hydrogen phosphate is used alone, no problem of corrosion resistance degradation occurs.

[0055] [Examples 8-13, Comparative Examples 8-17] ~Fully Aromatic Ether Ketone Resin Compositions~ In each of the examples and comparative examples, the raw material components shown in Tables 3 and 4 were mixed in the proportions shown in Tables 3 and 4 to obtain a powder of a fully aromatic ether ketone resin composition. Furthermore, the phosphorus stabilizer (B) used in each of the examples and comparative examples (except Comparative Example 17) is equivalent to any of the phosphorus stabilizers in Examples 1-7, Comparative Examples 1-7, and Reference Example 1, and their correspondence is shown below. Phosphorus stabilizers of Examples 8-13: These are the phosphorus stabilizers of Examples 1-6 (B). The phosphorus stabilizers (B) of Comparative Examples 8-12 are the phosphorus stabilizers (B) of Comparative Examples 1-5, respectively. Comparative Example 13 (B) phosphorus stabilizer: Example 7 (B) phosphorus stabilizer The phosphorus stabilizers (B) of Comparative Examples 14-15 are the phosphorus stabilizers (B) of Comparative Examples 6-7, respectively. Comparative Example 16 (B) phosphorus stabilizer: Refer to the phosphorus stabilizer of Example 1

[0056] Furthermore, the details of the fully aromatic ether ketone resin used are as follows. (A) Fully aromatic ether-ketone resin Polyetherketone (PEK) Polymerization is carried out according to the manufacturing method described in Japanese Patent Application No. 2009-227961 to obtain polyetherketone powder.

[0057] [evaluate] The following evaluation was conducted using the resin compositions obtained in the various examples and comparative examples.

[0058] (1) Preparation of resin composition pellets The powders of the fully aromatic ether ketone resin compositions obtained in the various examples and comparative examples were melt-mixed using a Coperion ZSK26MC twin-shaft extruder at a barrel set temperature of 380°C and a die set temperature of 400°C to obtain resin composition pellets.

[0059] (2) Melt viscosity retention rate For the obtained resin composition pellets, the melt viscosity was measured according to ISO 11443 using a CAPILOGRAPH 1B model manufactured by Toyo Seiki Co., Ltd., with a barrel temperature set at 400°C, an inner diameter of 1 mm, a length of 30 mm, and a shearing speed of 1000 rpm. The melt viscosity retention rate was calculated using the following formula (I). The calculated melt viscosity retention rates are shown in Tables 3 and 4. Melt viscosity retention rate (%) = [(melt viscosity at residence time of 30 minutes) / (melt viscosity at residence time of 10 minutes)] x 100···(I)

[0060] (3) Retention stability of melt viscosity The evaluation was based on the retention rate of melt viscosity calculated in each embodiment and comparative example. That is, a melt viscosity retention rate of 95% or more but less than 105% was evaluated as "good", and a retention rate of less than 95% or more than 105% was evaluated as "poor". When the evaluation result is "good", it indicates that the retention stability of melt viscosity is excellent. The evaluation results are shown in Tables 3 and 4.

[0061] (4) Manufacturability of the resin composition Based on the test results of the metal corrosion resistance of the phosphorus stabilizers in Examples 1-6, Comparative Examples 1-7, and Reference Example 1 above, the manufacturability of the resin compositions of each Example and Comparative Example was determined. That is, the phosphorus stabilizer corresponding to (B) used in each Example and Comparative Example was determined based on the test results of the metal corrosion resistance of the phosphorus stabilizers in Examples 1-6, Comparative Examples 1-7, and Reference Example 1. Specifically, a weight loss of 4% or less was evaluated as "good", and a weight loss of more than 4% was evaluated as "poor". When the evaluation result is "good", it indicates that the risk of corrosion of the manufacturing equipment is low, and therefore the manufacturability is excellent. The evaluation results are shown in Tables 3 and 4.

[0062] [Table 3]

[0063] [Table 4]

[0064] As shown in Tables 3 and 4, Examples 8-13 exhibit excellent retention stability of melt viscosity and manufacturability of the resin compositions. In contrast, Comparative Examples 8-17 do not simultaneously satisfy both retention stability of melt viscosity and manufacturability of the resin compositions. Furthermore, in Comparative Example 13, although the phosphorus stabilizer (B) of Example 7 was used, its content was too low, resulting in poor retention stability of melt viscosity. Similarly, in Comparative Example 16, since the phosphorus stabilizer (B) of Reference Example 1 was used, the metal corrosion resistance was good; however, the phosphorus stabilizer was only a hydrogen phosphate, and the pH was in the alkaline range (see Figure 1), resulting in poor retention stability of melt viscosity.

[0065] none

Claims

1. A fully aromatic ether ketone resin composition comprising (A) a fully aromatic ether ketone resin and (B) a phosphorus-based stabilizer, wherein the (B) phosphorus-based stabilizer contains (B1) a dihydrogen phosphate and (B2) a hydrogen phosphate, wherein the (B1) dihydrogen phosphate is one or more alkali metal dihydrogen phosphates, or one or more dihydrogen phosphates selected from the group consisting of alkaline earth metals and magnesium, and the (B2) hydrogen phosphate is one or more alkali metal hydrogen phosphates, or one or more hydrogen phosphates selected from the group consisting of alkaline earth metals and magnesium. When the (B1) dihydrogen phosphate is one or more alkali metal dihydrogen phosphates, the (B2) hydrogen phosphate is one or more hydrogen phosphates selected from the group consisting of alkaline earth metals and magnesium. When the (B1) dihydrogen phosphate is one or more dihydrogen phosphates selected from the group consisting of alkaline earth metals and magnesium, the (B2) hydrogen phosphate is one or more alkali metal hydrogen phosphates. The total content of the phosphorus stabilizers (B) mentioned above is 100 to 5000 ppm by mass.

2. The all-aromatic ether ketone resin composition as described in claim 1, wherein, In the phosphorus-based stabilizer (B) above, when the mole number of the alkali metal is set to [MI], the mole number of the metal selected from the group consisting of alkaline earth metals and magnesium is set to [MI II], and the mole number of phosphorus is set to [P], the following condition is satisfied: 1.00 < ([MI] + [MI II] × 2) / [P] < 2.

00.

3. The fully aromatic ether ketone resin composition as described in claim 1 or 2, wherein, In the phosphorus-based stabilizer (B) above, when the mole number of the alkali metal is set to [MI], the mole number of the metal selected from the group consisting of alkaline earth metals and magnesium is set to [MI II], and the mole number of phosphorus is set to [P], the following condition is satisfied: 1.10≤([MI]+[MI II]×2) / [P]≤1.

80.

4. The fully aromatic ether ketone resin composition as described in claim 1 or 2, wherein, The above-mentioned (A) all-aromatic ether ketone resin is selected from one or more of the group consisting of polyether ketone, polyether ether ketone and polyether ketone ether ketone.

5. The all-aromatic ether ketone resin composition as described in claim 1 or 2, wherein, The above-mentioned (B1) dihydrogen phosphate is a dihydrogen phosphate of one or more metals selected from the group consisting of sodium, potassium, magnesium and calcium, and the above-mentioned (B2) hydrogen phosphate is a hydrogen phosphate of one or more metals selected from the group consisting of sodium, potassium, magnesium and calcium.

6. The all-aromatic ether ketone resin composition as described in claim 1 or 2, wherein, The total content of the phosphorus stabilizers (B) mentioned above is 100 to 1000 ppm by mass.

7. The fully aromatic ether ketone resin composition as described in claim 1 or 2, wherein, The above-mentioned (A) all-aromatic ether ketone resin is polyether ketone.

8. A molded article formed from a fully aromatic ether ketone resin composition as described in claim 1 or 2.

9. A phosphorus-based stabilizer comprising (B1) dihydrogen phosphate and (B2) hydrogen phosphate, wherein the (B1) dihydrogen phosphate is one or more alkali metal dihydrogen phosphates, or one or more dihydrogen phosphates selected from the group consisting of alkaline earth metals and magnesium; the (B2) hydrogen phosphate is one or more alkali metal hydrogen phosphates, or one or more hydrogen phosphates selected from the group consisting of alkaline earth metals and magnesium; when the (B1) dihydrogen phosphate is one or more alkali metal dihydrogen phosphates, the (B2) hydrogen phosphate is one or more hydrogen phosphates selected from the group consisting of alkaline earth metals and magnesium; when the (B1) dihydrogen phosphate is one or more dihydrogen phosphates selected from the group consisting of alkaline earth metals and magnesium, the (B2) hydrogen phosphate is one or more alkali metal hydrogen phosphates.

10. The phosphorus-based stabilizer as described in claim 9, wherein, When the mole number of alkali metals is set to [MI], the mole number of metals selected from the group consisting of alkaline earth metals and magnesium is set to [MI II], and the mole number of phosphorus is set to [P], the following condition is satisfied: 1.00 < ([MI] + [MI II] × 2) / [P] < 2.

00.

11. The phosphorus-based stabilizer as described in claim 9 or 10, wherein, The above-mentioned (B1) dihydrogen phosphate is a dihydrogen phosphate of one or more metals selected from the group consisting of sodium, potassium, magnesium and calcium, and the above-mentioned (B2) hydrogen phosphate is a hydrogen phosphate of one or more metals selected from the group consisting of sodium, potassium, magnesium and calcium.

12. The phosphorus-based stabilizer as described in claim 9 or 10, wherein, When the mole number of alkali metals is set to [MI], the mole number of metals selected from the group consisting of alkaline earth metals and magnesium is set to [MI II], and the mole number of phosphorus is set to [P], the following condition is satisfied: 1.10≤([MI]+[MI II]×2) / [P]≤1.80.

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