JP2013006987A - Resin composition highly filled with filler, method for producing tablet, and formed article comprising the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition highly filled with a filler, which can be melt-formed, exhibits no metal mold corrosion in processing, can exhibit filler properties highly efficiently, and is excellent in the balance of formation processability and physical properties; and to provide a formed article obtained therefrom.SOLUTION: The resin composition highly filled with a filler is prepared by blending (a) 5 to 50 vol.% of a polyphenylene ether ketone having a reduced viscosity in the range of 0.6 to 2.5 dL/g as measured in a 98-wt.% sulfuric acid at 25°C in a concentration of 0.1 g/dL, and (b) 95 to 50 vol% of an inorganic filler, wherein the total of (a) and (b) is 100 vol.%.

Description

  The present invention relates to a highly filled thermoplastic resin composition that has no mold corrosion during molding, has an excellent balance between molding processability and physical properties, and can exhibit the properties of the filler with high efficiency. .

  Engineer plastics have been actively pioneered in fields where resinization has been difficult until now, and the required performance of these resins is becoming increasingly diverse and stricter.

  In recent years, due to the diversification of designs, the degree of freedom of the shape of molded products has been required. However, the conventionally used metal has a limit in the degree of freedom of a molded product. Thus, studies have been made on filler (filler) reinforced thermoplastic resins for metal replacement. For example, the properties required for each application, such as thermal conductivity, high strength and high rigidity, and dimensional accuracy at high temperatures, are not satisfied by conventional filler-reinforced thermoplastic resins, and further improvements in properties are required. It has become like this. In particular, it has been demanded to increase the output of electrical control components such as a CPU of a personal computer, to maintain mechanical strength in a high temperature atmosphere due to heat when using laser light, and to reduce changes in characteristics due to temperature. In particular, since it is in a high-temperature atmosphere, a method for imparting heat dissipation properties to a resin has been proposed.

  Polyphenylene ether ether ketone resin has extremely suitable properties as engineering plastics such as excellent heat resistance, chemical resistance, moist heat resistance, flame resistance, non-elution of impurities, wear resistance, slidability, and radiation resistance. Resin. In particular, polyetheretherketone resin (hereinafter sometimes abbreviated as PEEK resin) can be molded into various molded parts, films, sheets, fibers, etc. by melt molding processing methods such as injection molding and extrusion molding. Demand for high heat resistance, chemical resistance, and low contamination is increasing in electrical and electronic parts, mechanical parts, and automotive parts of reinforced and filler-reinforced PEEK resin compositions. The creation of a highly functional PEEK resin composition highly filled with a filler is desired.

  From the viewpoint of high filling of the filler to the PEEK resin, Patent Document 1 discloses a high filling PEEK resin obtained by blending 30 to 70% by weight of a filler with a low viscosity PEEK resin. However, since low-viscosity PEEK is used as the matrix resin, there is a drawback that depending on the type of filler, the mechanical strength of the high-filled resin molded product is low, and desired characteristics cannot be obtained. Also, low-viscosity PEEK is not preferred because it has many gas components at the time of molding due to the increase in end groups, causing mold corrosion and electrical / electronic circuit contact failure.

  Patent Documents 2 and 3 disclose PEEK resin compositions containing 40-60% by volume of PEEK resin, including a reinforcing fiber filler and an immobilizing filler for the purpose of restraining amorphous parts. The resin composition tends to have a high viscosity due to the high blending of the immobilizing filler, and there is a disadvantage that the molding processability is poor. In addition, the characteristics obtained by high filler filling have not been clarified except for the improvement of the heat deflection temperature (HDT).

  On the other hand, from the viewpoint of a highly filled resin composition of filler, Patent Document 4 discloses a highly filled resin obtained by blending 50 to 95% by volume of an inorganic filler with a polyarylene sulfide resin obtained by ring-opening polymerization of a cyclic polyarylene sulfide. Although a composition is disclosed, there is no description about resins other than polyarylene sulfide, and the effect is unknown.

  Recently, aromatic cyclic compounds have the potential to be applied to highly functional materials and functional materials based on the properties resulting from their cyclic properties, for example, properties as inclusion compounds, and high molecular weight straight-through by ring-opening polymerization. In recent years, it has attracted attention for its specificity derived from its structure, such as its use as an effective monomer for the synthesis of chain polymers. Cyclic polyphenylene ether ether ketone also belongs to the category of aromatic cyclic compounds, and is a notable compound as described above, and is regarded as a promising technique for enhancing PEEK functionality.

  For example, Non-Patent Document 1 discloses a synthesis method of cyclic polyphenylene ether ether ketone and the characteristics of the product. Specifically, linear polyphenylene ether ether ketone oligomer having hydroxyl groups at both ends and fluorine groups at both ends are disclosed. A linear polyether obtained by ring-opening polymerization of a cyclic polyether ether ketone obtained by this method is described. There was no description of ether ketone and its highly filled resin composition, and its properties were completely unknown.

  From the above, there has been no filler high-filling PEEK resin composition that can sufficiently meet market demands so far, and creation of a highly-filled and highly functional PEEK resin composition by a method different from the prior art is desired. It was.

Special table 2007-506833 Japanese National Patent Publication No. 11-507663 JP 2006-291217 A JP 2008-231138 A

Macromolecules, 29, 5502 (1996)

  The present invention has a good flow rate without molding corrosion during molding, and the resulting molded product has high strength, enabling the properties of the blended fillers to be exhibited with high efficiency, which is unprecedented high filling It is an object to provide a thermoplastic resin composition and a molded product thereof.

The inventors of the present invention have arrived at the present invention as a result of intensive studies in order to solve the above problems.
That is, the present invention
(1) The total viscosity of (a) and (b) is 100% by volume, and (a) the reduced viscosity measured in a 98% by weight sulfuric acid at a concentration of 0.1 g / dL and 25 ° C. is 0.6-2. Highly filled resin composition comprising 5-50% by volume of polyphenylene ether ether ketone in the range of 5 dL / g and (b) 95-50% by volume of inorganic filler,
(2) The polyphenylene ether ether ketone is obtained by ring-opening polymerization of a composition containing 60% by weight or more of a cyclic polyphenylene ether ether ketone represented by the following general formula (I): 1) Filler highly filled resin composition according to 1),

(M is an integer of 2 to 40, and a mixture of compounds in which m is any of 2 to 40 may be used.)
(3) (b) The ratio (D90 / D10) of the 90% cumulative particle size (D90) and the 10% cumulative particle size (D10) obtained from the cumulative particle size distribution curve of the inorganic filler is 10 or more. The filler high-filling resin composition according to any one of (1) or (2),
(4) Further, (c) at least one of fatty acid metal salt, ester compound, amide group-containing compound, epoxy compound, and phosphate ester is added to 100 parts by weight of the total amount of (a) and (b). The filler high-filling resin composition according to any one of (1) to (3) above, wherein 0.5 to 10 parts by weight of the filler is blended.
(5) The filler high-filling resin composition according to any one of the above (1) to (4) is compression-molded in a solid phase to form a tablet. Tablet manufacturing method,
(6) A tablet obtained by compression-molding the highly filled resin composition according to any one of (1) to (4) in a solid phase,
(7) A molded article obtained by injection-molding the filler-filled resin composition according to any one of (1) to (4) or the tablet according to (6),
(8) Cyclic polyphenylene ether ether ketone containing 60% by weight or more of cyclic polyphenylene ether ether ketone represented by the following general formula (I), where the sum of (a ′) and (b) is 100% by volume: A method for producing a filler-filled resin composition, comprising 5 to 50% by volume of the composition and (b) 95 to 50% by volume of an inorganic filler and then ring-opening polymerization in the presence of a catalyst or an initiator,

(M is an integer of 2 to 40, and a mixture of compounds in which m is any of 2 to 40 may be used.)
(9) (b) The ratio (D90 / D10) of the 90% cumulative particle size (D90) and the 10% cumulative particle size (D10) obtained from the cumulative particle size distribution curve of the inorganic filler is 10 or more. The manufacturing method of the highly filled resin composition as described in said (8) is provided.

  The present invention has no mold corrosion at the time of molding, and is a highly filled resin composition, but it has good flow, and the obtained molded product exhibits the characteristics of the filler used at high strength with high efficiency. It is possible to obtain a highly filled thermoplastic resin composition and a molded product thereof that could not be obtained in the past.

  Hereinafter, the present invention will be described in detail.

(1) Cyclic polyphenylene ether ether ketone The cyclic polyphenylene ether ether ketone in the present invention is a cyclic compound represented by the following general formula (I) having paraphenylene ketone and paraphenylene ether as repeating structural units.

  The range of the repeating number m in the formula (I) is 2 to 40, more preferably 2 to 20, further preferably 2 to 15, and 2 to 10 can be exemplified as a particularly preferable range. Since the melting point of the cyclic polyphenylene ether ether ketone tends to increase as the repeating number m increases, the repeating number m is preferably within the above range from the viewpoint of melting and dissolving the cyclic polyphenylene ether ether ketone at a low temperature.

  Further, the cyclic polyphenylene ether ether ketone represented by the formula (I) is preferably a mixture having a different repeating number m, and at least a cyclic polyphenylene ether ether ketone mixture having three or more different repeating numbers m. More preferably, it is more preferably a mixture consisting of 4 or more repeating numbers m, and particularly preferably a mixture consisting of 5 or more repeating numbers m. Furthermore, it is particularly preferable that these repeating numbers m are continuous. Compared to a single compound having a single repeating number m, the melting point of a mixture consisting of a different repeating number m tends to be lower, and compared to a cyclic polyphenylene ether ether ketone mixture consisting of two different repeating numbers m. The melting point of a mixture consisting of 3 or more repeating m tends to be lower, and the melting point of a mixture consisting of continuous repeating number m tends to be lower than that of a mixture consisting of discontinuous repeating number m. It is in. Here, the cyclic polyphenylene ether ether ketone having each repeating number m can be analyzed by component separation by high performance liquid chromatography, and the composition of the cyclic polyphenylene ether ether ketone, that is, each repeating contained in the cyclic polyphenylene ether ether ketone. The weight fraction of the cyclic polyphenylene ether ether ketone having a number m can be calculated from the peak area ratio of each cyclic polyphenylene ether ether ketone in high performance liquid chromatography.

  Furthermore, the cyclic polyphenylene ether ether ketone composition of the present invention preferably has a melting point of 270 ° C. or lower. In this case, the melting point is significantly lower than that of the corresponding linear polyphenylene ether ether ketone. The melting point is more preferably 250 ° C. or less, and further preferably 230 ° C. or less. The lower the melting point of the cyclic polyphenylene ether ether ketone composition, the lower the processing temperature, and the lower the process temperature when the cyclic polyphenylene ether ether ketone is converted to polyphenylene ether ether ketone by ring-opening polymerization. Therefore, it is advantageous from the viewpoint that the energy required for processing can be reduced. In addition, by setting the process temperature low, undesirable side reactions such as decomposition reaction and crosslinking reaction are suppressed, and it becomes possible to obtain a higher quality polyphenylene ether ether ketone resin. Here, the melting point of the cyclic polyphenylene ether ether ketone composition can be measured by observing the endothermic peak temperature using a differential scanning calorimeter.

  Further, the cyclic polyphenylene ether ether ketone composition in the present invention is a cyclic polyphenylene ether ether ketone composition containing 60% by weight or more of cyclic polyphenylene ether ether ketone, more preferably a composition containing 65% by weight or more, More preferably, the composition contains more than 75% by weight, and more preferably more than 75% by weight. As an impurity component in the cyclic polyphenylene ether ether ketone composition, that is, a component other than the cyclic polyphenylene ether ether ketone, linear polyphenylene ether ether ketone can be mainly exemplified. Since the linear polyphenylene ether ether ketone has a high melting point, the melting point of the cyclic polyphenylene ether ether ketone composition tends to increase as the weight fraction of the linear polyphenylene ether ether ketone increases. Therefore, when the weight fraction of the cyclic polyphenylene ether ether ketone in the cyclic polyphenylene ether ether ketone composition is in the above range, it tends to be a cyclic polyphenylene ether ether ketone composition having a low melting point, and further the cyclic polyphenylene ether ether ketone composition. When the product is used as a polyphenylene ether ether ketone prepolymer, the weight content of the cyclic polyphenylene ether ether ketone in the cyclic polyphenylene ether ether ketone composition is also obtained from the viewpoint of obtaining a polyphenylene ether ether ketone having a sufficiently high degree of polymerization. The rate is preferably in the above range.

The reduced viscosity (η) of the cyclic polyphenylene ether ether ketone composition of the present invention having the characteristics as described above is preferably 0.1 dL / g or less, and preferably 0.09 dL / g or less. More preferably, it is more preferably 0.08 dL / g or less. The reduced viscosity in the present invention is a concentration of 0.1 g / dL (cyclic polyphenylene ether ether ketone composition or linear polyphenylene ether ether ketone weight / 98 wt% concentrated sulfuric acid capacity) unless otherwise specified. It is a value measured with an Ostwald viscometer at 25 ° C. immediately after completion of dissolution for the sulfuric acid solution to minimize the effect of sulfonation. The reduced viscosity was calculated according to the following formula.
η = {(t / t ₀ ) −1} / C
(Where t is the number of seconds that the sample solution passes, t ₀ is the number of seconds that the solvent (98 wt% concentrated sulfuric acid) passes, and C is the concentration of the solution).

  As a method for producing the cyclic polyphenylene ether ether ketone composition of the present invention, any method can be used as long as the cyclic polyphenylene ether ether ketone composition having the above-described characteristics can be produced, but (a) at least a dihalogenated aromatic ketone is preferred as the preferred method. (B) heating a mixture containing at least a dihalogenated aromatic ketone compound, a base, a dihydroxy aromatic compound, and an organic polar solvent, by heating and reacting the mixture containing the compound, the base, and the organic polar solvent; It is possible to use the manufacturing method by making it react.

  Here, specific examples of the dihalogenated aromatic ketone compound include 4,4′-difluorobenzophenone, 4,4′-dichlorobenzophenone, 4,4′-dibromobenzophenone, 4,4′-diiodobenzophenone, 4- Fluoro-4′-chlorobenzophenone, 4-fluoro-4′-bromobenzophenone, 4-fluoro-4′-iodobenzophenone, 4-chloro-4′-bromobenzophenone, 4-chloro-4′-iodobenzophenone, 4- Examples include bromo-4'-iodobenzophenone, 1,4-bis (4-fluorobenzoyl) benzene, 1,4-bis (4-chlorobenzoyl) benzene, and among these, 4,4'-difluorobenzophenone, 4 , 4'-dichlorobenzophenone, 1,4-bis (4-fluorobenzoy ) Benzene and 1,4-bis (4-chlorobenzoyl) benzene are preferred, 4,4′-difluorobenzophenone and 4,4′-dichlorobenzophenone are more preferred, and 4,4′-difluorobenzophenone is more preferred. Can be mentioned.

  Bases include alkaline metal carbonates such as lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate, alkaline earth metal carbonates such as calcium carbonate, strontium carbonate, barium carbonate, lithium hydrogen carbonate, hydrogen carbonate Alkali metal bicarbonates such as sodium, potassium bicarbonate, rubidium bicarbonate, cesium bicarbonate, alkaline earth metal bicarbonates such as calcium bicarbonate, strontium bicarbonate, barium bicarbonate, or lithium hydroxide, water Examples include alkali metal hydroxides such as sodium oxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, and alkaline earth metal hydroxides such as calcium hydroxide, strontium hydroxide, and barium hydroxide. Above all, from the viewpoint of economy and responsiveness Sodium acid, carbonates such as potassium carbonate and sodium hydrogen carbonate, bicarbonates such as potassium hydrogen carbonate are preferable, sodium carbonate, potassium carbonate is used more preferably. These may be used alone or in combination of two or more. The alkali is preferably used in the form of an anhydride, but can also be used as a hydrate or an aqueous mixture. Here, the aqueous mixture refers to an aqueous solution, a mixture of an aqueous solution and a solid component, or a mixture of water and a solid component.

  In addition, the organic polar solvent used in the production of the cyclic polyphenylene ether ether ketone composition of the present invention does not substantially cause undesirable side reactions such as reaction inhibition and decomposition of the generated cyclic polyphenylene ether ether ketone. If there is no particular limitation. Specific examples of such organic polar solvents include N-methyl-2-pyrrolidone, N-methylcaprolactam, N, N-dimethylformamide, N, N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone. Nitrogen-containing polar solvents such as hexamethylphosphoramide and tetramethylurea, sulfoxide and sulfone solvents such as dimethyl sulfoxide, dimethyl sulfone, diphenyl sulfone and sulfolane, nitrile solvents such as benzonitrile, diaryl ethers such as diphenyl ether, Examples thereof include ketones such as benzophenone and acetophenone, and mixtures thereof. These are preferably used because of their high reaction stability. Among them, N-methyl-2-pyrrolidone and dimethyl sulfoxide are preferred, and N-methyl-2-pyrrolidone is particularly preferred. These organic polar solvents are excellent in stability in a high temperature region, and can be said to be preferable organic polar solvents from the viewpoint of availability.

  Specific examples of the dihydroxy aromatic compound used in the present invention include hydroquinone, 4,4′-dihydroxybenzophenone, and 1,4-bis (4-hydroxybenzoyl) benzene. Hydroquinone or 4,4 ′ -Dihydroxybenzophenone is more preferred, and hydroquinone is particularly preferred. These dihydroxy aromatic compounds may be used alone or as a mixture of two or more.

  The amount of the organic polar solvent in the mixture when producing the cyclic polyphenylene ether ether ketone composition by the method according to the production method (a) or (b) is preferably relative to 1.0 mol of the benzene ring component in the mixture. 1.15 liters or more, more preferably 1.30 liters or more, further preferably 1.50 liters or more, and particularly preferably 2.0 liters or more. The upper limit of the amount of the organic polar solvent in the mixture is not particularly limited, but is preferably 100 liters or less, more preferably 50 liters or less, and more preferably 20 liters or less with respect to 1.0 mol of the benzene ring component in the mixture. Is more preferable, and 10 liters or less is particularly preferable. Increasing the amount of the organic polar solvent tends to improve the selectivity of cyclic polyphenylene ether ether ketone production, but if too much, the production amount of cyclic polyphenylene ether ether ketone per unit volume of the reaction vessel tends to decrease. In addition, the time required for the reaction tends to increase. Therefore, from the viewpoint of achieving both the production selectivity of the cyclic polyphenylene ether ether ketone and the productivity, the use range of the organic polar solvent described above is preferable. The amount of the organic polar solvent here is based on the volume of the solvent under normal temperature and normal pressure. The amount of the organic polar solvent used in the reaction mixture is the amount of the organic polar solvent introduced into the reaction system during the dehydration operation. It is the amount obtained by subtracting the amount of the organic polar solvent excluded from the reaction system. In addition, the benzene ring component in the mixture here is a benzene ring component contained in a raw material that can become a cyclic polyphenylene ether ether ketone constituent by reaction, and the “number of moles” of the benzene ring component in these raw materials means “compound Represents the number of benzene rings comprising For example, 4,4'-difluorobenzophenone has 2 moles of benzene ring component, 1 mole of hydroquinone has 1 mole of benzene ring component, and a mixture containing 1 mole of 4,4'-difluorobenzophenone and 1 mole of hydroquinone has 3 moles of benzene ring component. Calculate with the mixture containing. In addition, the component which cannot become a cyclic polyphenylene ether ether ketone constituent by reaction, such as toluene, is considered as 0 mol of benzene ring components.

  The amount of base used in the method (a) for producing a cyclic polyphenylene ether ether ketone composition by heating and reacting a mixture containing at least a dihalogenated aromatic ketone compound, a base, and an organic polar solvent is a dihalogenated aromatic ketone. The ratio may be a ratio larger than the stoichiometric ratio with respect to the compound, and the specific amount of base used is, for example, the amount of divalent base used, such as sodium carbonate or potassium carbonate, A mole, sodium bicarbonate or When the use amount of a monovalent base such as potassium hydrogen carbonate is B mol, 1.0 mol of the dihalogenated aromatic ketone compound used in producing the cyclic polyphenylene ether ether ketone composition by the production method (a). (A + 2B) is preferably in the range of 1.00 mol to 1.25 mol, More preferably in a 1.15 mols, even more preferred examples in a range of 1.10 mol 1.00 mol.

  On the other hand, use of a base in the production method (b) of the cyclic polyphenylene ether ether ketone composition by heating and reacting a mixture containing at least a dihalogenated aromatic ketone compound, a base, a dihydroxy aromatic compound, and an organic polar solvent. The amount may be a ratio larger than the stoichiometric ratio with respect to the dihydroxy aromatic compound, and the specific amount of the base used is (A + 2B) from 1.00 to 1.10 mol with respect to the dihydroxy aromatic compound. It is preferably in the range of 1.00, more preferably in the range of 1.00 to 1.05 mol, and still more preferably in the range of 1.00 to 1.03 mol. In addition, when a separately prepared metal salt of a dihydroxy aromatic compound is used in the production of the cyclic polyphenylene ether ether ketone composition by the production method (b), an additional amount of base is added. Can be supplied. The excess amount of the supplied base is such that (A + 2B) is in the range of 0 to 0.10 mol with respect to 1.0 mol of the dihydroxy aromatic compound used for producing the cyclic polyphenylene ether ether ketone composition. Preferably, it is preferably in the range of 0 to 0.05 mol, more preferably in the range of 0 to 0.03 mol. When the amount of the base used in producing the cyclic polyphenylene ether ether ketone composition in the production method (b) is within these suitable ranges, it is possible to sufficiently generate the metal salt of the dihydroxy aromatic compound, Furthermore, it is preferable because the progress of an undesirable reaction such as a decomposition reaction of the generated cyclic polyphenylene ether ether ketone by a large excess of base can be suppressed.

  The reaction temperature at which a mixture containing at least a dihalogenated aromatic ketone compound, a base, and an organic polar solvent, or a mixture containing at least a dihalogenated aromatic ketone compound, a base, a dihydroxy aromatic compound, and an organic polar solvent is reacted by heating. The dihalogenated aromatic ketone compound used in the reaction, the base, and the organic polar solvent, and further dihydroxyaromatic compound can be diversified depending on the type and amount, but cannot be uniquely determined, but usually 120 to 350 ° C., preferably 130 The range of -320 degreeC, More preferably, 140-300 degreeC can be illustrated. In this preferable temperature range, a higher reaction rate tends to be obtained. The reaction may be either a one-step reaction performed at a constant temperature, a multi-stage reaction in which the temperature is raised stepwise, or a reaction in which the temperature is continuously changed.

  The reaction time depends on the type and amount of the raw material used or the reaction temperature, and thus cannot be specified unconditionally, but is preferably 0.1 hour or longer, more preferably 0.5 hour or longer, and further preferably 1 hour or longer. . By setting it as this preferable time or more, it exists in the tendency which can reduce an unreacted raw material component fully. On the other hand, there is no particular upper limit for the reaction time, but the reaction proceeds sufficiently even within 40 hours, preferably within 10 hours, more preferably within 6 hours.

  When reacting by heating a mixture containing at least a dihalogenated aromatic ketone compound, a base, and an organic polar solvent, or heating a mixture containing at least a dihalogenated aromatic ketone compound, a base, a dihydroxy aromatic compound, and an organic polar solvent In the reaction, it is also possible to add to the mixture components other than the essential components that do not significantly inhibit the reaction and components that have an effect of accelerating the reaction. Moreover, there is no restriction | limiting in particular in the method of performing reaction, However, It is preferable to carry out on stirring conditions. Furthermore, in the method for producing the cyclic polyphenylene ether ether ketone composition of the present invention, various known polymerization methods and reaction methods such as a batch method and a continuous method can be employed. In addition, the atmosphere in the production is preferably a non-oxidizing atmosphere, preferably in an inert atmosphere such as nitrogen, helium, and argon, and preferably in a nitrogen atmosphere in view of economy and ease of handling.

  In addition, in the above reaction, when a large amount of water is present in the reaction system, adverse effects such as a decrease in reaction rate and the generation of a side reaction product that is difficult to separate from cyclic polyphenylene ether ether ketone tend to become apparent. Therefore, it is important to exclude from the reaction system water in the case where a hydrate or an aqueous mixture is used as a base or water by-produced by the reaction. The amount of water present in the system during the reaction is preferably 2.0% by weight or less, more preferably 1.0% by weight or less, and more preferably 0.5% by weight or less, The content is particularly preferably 0.1% by weight or less, and it is important to perform a dehydration operation as necessary so as to be within this preferable range. Here, the amount of water present in the system is a weight fraction with respect to the total weight of the reaction mixture, and the amount of water can be measured by the Karl Fischer method. Although there is no restriction | limiting in particular in the time which performs dehydration operation, (a) After mixing essential components in a manufacturing method (a) or (b), or (b) After mixing essential components other than a dihalogenated aromatic ketone compound It is preferable that Here, when the dehydration operation is performed by the method according to (a), a dihalogenated aromatic ketone compound or a dihalogenated aromatic ketone compound and an organic polar solvent are added after the dehydration operation to produce a cyclic polyphenylene ether ether ketone composition. I do. As a method for removing water, any method can be used as long as water can be removed from the reaction system, and examples thereof include dehydration by high-temperature heating and azeotropic distillation using an azeotropic solvent, and in particular, from the viewpoint of dehydration efficiency. A preferred method is an azeotropic distillation method. Here, the azeotropic solvent used in the azeotropic distillation is an organic compound that can form an azeotropic mixture with water, and the boiling point of the azeotropic mixture is lower than the boiling point of the organic polar solvent used in the reaction. Specific examples include hydrocarbon solvents such as hexane, cyclohexane, heptane, benzene, toluene and xylene, and inert chlorinated aromatic compounds such as chlorobenzene and dichlorobenzene, among which toluene and xylene Can be mentioned as a preferred azeotropic solvent. In addition, the amount of azeotropic solvent cannot be specified unconditionally because the amount required to form an azeotrope with water varies depending on the amount of water present in the system and the type of solvent. It is preferable to use an excess amount of solvent more than that required to remove water as an azeotrope, specifically 0.2 liters or more per 1.0 mole of dihalogenated aromatic ketone compound in the mixture. Is preferably 0.5 liters or more, more preferably 1.0 liters or more. Further, the upper limit of the amount of azeotropic solvent is not particularly limited, but it is preferably 20.0 liters or less, preferably 10.0 liters or less, relative to 1.0 mol of the dihalogenated aromatic ketone compound in the mixture. More preferably, it is more preferably 5.0 liters or less. When the amount of the azeotropic solvent used is too large, the polarity of the mixture decreases, so that the efficiency of the reaction between the base and the dihalogenated aromatic ketone compound or the reaction between the base and the dihydroxy aromatic compound tends to decrease. Here, the amount of the azeotropic solvent is based on the volume of the solvent under normal temperature and pressure. In addition, when performing azeotropic distillation of water using the principle of the Dean-Stark device, the amount of azeotropic solvent in the reaction system can always be kept constant, so the amount of azeotropic solvent used can be further reduced. It is. The temperature at which water is removed from the reaction system cannot be uniquely determined because the boiling point of the azeotrope with water differs depending on the type of azeotropic solvent, but it is above the boiling point of the azeotrope with water and is It is preferable that it is below the boiling point of the organic polar solvent used for this, Specifically, the range of 60-170 degreeC can be illustrated, Preferably it is 80-170 degreeC, More preferably, it is 100-170 degreeC, More preferably, it is 120-170 degreeC. The range of can be illustrated. The removal of water may be either a method of performing a constant temperature within a preferable temperature range, a method of increasing the temperature stepwise, or a method of changing the temperature continuously. Furthermore, it is also a preferable method to carry out the azeotropic distillation under reduced pressure. By performing the azeotropic distillation under reduced pressure, water tends to be removed more efficiently.

  The azeotropic solvent is preferably excluded from the system after azeotropic distillation. The time for removing the azeotropic solvent from the system is preferably after the end of the azeotropic distillation of water. Further, when the dehydration operation is performed by the method according to (a) above, the removal of the azeotropic solvent is performed by dihalogenated aromatic. It is preferable to carry out the step before adding the ketone compound or the dihalogenated aromatic ketone compound and the organic polar solvent. If a large amount of the azeotropic solvent remains in the system, the polarity of the reaction system tends to decrease, and the reaction rate for producing the cyclic polyphenylene ether ether ketone tends to decrease. Therefore, an operation for removing the azeotropic solvent is necessary. The amount of azeotropic solvent present in the system during the cyclic polyphenylene ether ether ketone formation reaction is preferably 20% or less, preferably 10% or less, relative to the organic polar solvent used in the cyclic polyphenylene ether ether ketone formation reaction. Is more preferably 8% or less, and particularly preferably 6% or less. It is important to remove the azeotropic solvent so that it is below this preferred range. As a method for removing the azeotropic solvent, a method by distillation is preferable, and an inert gas such as nitrogen, helium, or argon may be used as a carrier gas. In addition, distillation under reduced pressure is also a preferable method, and the azeotropic solvent tends to be removed more efficiently. Further, the temperature at which the azeotropic solvent is removed may be any temperature as long as the azeotropic solvent can be excluded from the reaction system. Specifically, a range of 60 to 170 ° C. can be exemplified, preferably 100 to 170 ° C., more preferably. Can be exemplified by the range of 120 to 170 ° C, more preferably 140 to 170 ° C. The removal of the azeotropic solvent may be performed either at a constant temperature in a preferred temperature range, a method of increasing the temperature stepwise, or a type of continuously changing the temperature.

  The cyclic polyphenylene ether ether ketone composition of the present invention can be obtained by separating and recovering from the reaction mixture obtained by the production method described above. The reaction mixture obtained by the above production method contains at least cyclic polyphenylene ether ether ketone, linear polyphenylene ether ether ketone and an organic polar solvent, and other components include unreacted raw materials, by-product salts, water, azeotropic solvents, and the like. May be included. The method for recovering the cyclic polyphenylene ether ether ketone from such a reaction mixture is not particularly limited. For example, if necessary, after removing a part or most of the organic polar solvent by an operation such as distillation, the polyphenylene ether ether ketone component The cyclic polyphenylene ether ether ketone is mixed with a linear polyphenylene ether ether ketone by mixing with a solvent having low solubility with respect to the organic solvent and having solubility in the by-product salt, if necessary, under heating. A method of recovering as a mixed solid can be exemplified. Solvents having such characteristics are generally relatively polar solvents, and preferred solvents differ depending on the type of organic polar solvent and by-product salt used, but are not limited. For example, water, methanol, ethanol, propanol, isopropanol , Alcohols represented by butanol and hexanol, acetone, ketones represented by methyl ethyl ketone, acetates represented by ethyl acetate, butyl acetate, etc., and water, methanol and Acetone is preferred and water is particularly preferred.

  By performing the treatment with such a solvent, it is possible to reduce the amount of organic polar solvent or by-product salt contained in the mixed solid of cyclic polyphenylene ether ether ketone and linear polyphenylene ether ether ketone. Since cyclic polyphenylene ether ether ketone and linear polyphenylene ether ether ketone are both precipitated as solid components by this treatment, a mixture of cyclic polyphenylene ether ether ketone and linear polyphenylene ether ether ketone can be recovered by a known solid-liquid separation method. Is possible. Examples of the solid-liquid separation method include separation by filtration, centrifugation, and decantation. Note that these series of treatments can be repeated several times as necessary, whereby an organic polar solvent or by-product salt contained in a mixed solid of cyclic polyphenylene ether ether ketone and linear polyphenylene ether ether ketone is thereby obtained. The amount tends to be further reduced.

  Moreover, as a processing method by said solvent, there exists the method of mixing a solvent and a reaction mixture, and it is also possible to stir or heat suitably as needed. Although there is no restriction | limiting in particular in the temperature at the time of processing with a solvent, The range of 20-220 degreeC is preferable, and the range of 50-200 degreeC is further more preferable. In such a range, for example, by-product salt can be easily removed, and the treatment can be performed at a relatively low pressure, which is preferable. Here, when water is used as the solvent, the water is preferably distilled water or deionized water, but if necessary, formic acid, acetic acid, propionic acid, butyric acid, chloroacetic acid, dichloroacetic acid, acrylic acid, crotonic acid, Organic acidic compounds such as benzoic acid, salicylic acid, oxalic acid, malonic acid, succinic acid, phthalic acid, fumaric acid, and alkali metal salts and alkaline earth metal salts thereof, sulfuric acid, phosphoric acid, hydrochloric acid, carbonic acid, silicic acid, etc. It is also possible to use an aqueous solution containing an inorganic acidic compound and ammonium ions. If the mixed solid of cyclic polyphenylene ether ether ketone and linear polyphenylene ether ether ketone obtained after this treatment contains the solvent used in the treatment, drying may be performed as necessary to remove the solvent. Is possible.

  In the recovery method described above, the cyclic polyphenylene ether ether ketone is recovered as a mixture with the linear polyphenylene ether ether ketone to obtain a cyclic polyphenylene ether ether ketone composition. In order to further increase the content of cyclic polyphenylene ether ether ketone in this composition, as a method for separating and recovering cyclic polyphenylene ether ether ketone from this mixture, for example, solubility of cyclic polyphenylene ether ether ketone and linear polyphenylene ether ether ketone is used. And more specifically, a solvent having a high solubility in cyclic polyphenylene ether ether ketone and a poor solubility in linear polyphenylene ether ether ketone is treated with the cyclic polyphenylene under heating as necessary. An example is a method in which cyclic polyphenylene ether ether ketone is obtained as a solvent-soluble component by contacting with a mixture of ether ether ketone and linear polyphenylene ether ether ketone. In general, linear polyphenylene ether ether ketone is known to have high crystallinity and very low solubility in solvents. Solubility of cyclic polyphenylene ether ether ketone and linear polyphenylene ether ether ketone in solvents Since the difference in properties is large, it is possible to efficiently obtain a cyclic polyphenylene ether ether ketone by the separation method using the difference in solubility.

  The solvent used here is not particularly limited as long as it is a solvent capable of dissolving cyclic polyphenylene ether ether ketone, but cyclic polyphenylene ether ether ketone dissolves in the dissolving environment, but linear polyphenylene ether ether ketone is difficult to dissolve. A solvent is preferable, and a solvent that does not dissolve linear polyphenylene ether ether ketone is more preferable. The reaction system pressure when the mixture of the cyclic polyphenylene ether ether ketone and the linear polyphenylene ether ether ketone is brought into contact with the solvent is preferably normal pressure or slight pressure, and particularly preferably normal pressure. There is an advantage that the components of the reactor for constructing it are inexpensive. From this point of view, it is desirable that the reaction system pressure avoid pressurizing conditions that require expensive pressure resistant containers. As the solvent to be used, those which do not substantially cause an undesirable side reaction such as decomposition or crosslinking of the polyphenylene ether ether ketone component are preferable, and a solvent which is preferable when the operation of bringing the mixture into contact with the solvent is performed, for example, under normal pressure reflux conditions. As hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane, cyclopentane, benzene, toluene, xylene, chloroform, bromoform, methylene chloride, 1,2-dichloroethane, 1,1,1-trichloroethane, chlorobenzene Halogen solvents such as 2,6-dichlorotoluene, ether solvents such as diethyl ether, tetrahydrofuran and diisopropyl ether, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, Examples include polar solvents such as limethyl phosphoric acid and N, N-dimethylimidazolidinone, among which benzene, toluene, xylene, chloroform, bromoform, methylene chloride, 1,2-dichloroethane, 1,1,1-trichloroethane, chlorobenzene 2,6-dichlorotoluene, diethyl ether, tetrahydrofuran, diisopropyl ether, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, trimethyl phosphoric acid, N, N-dimethylimidazolidinone are preferred, toluene, More preferred examples are xylene, chloroform, methylene chloride and tetrahydrofuran.

  There is no particular limitation on the atmosphere when the mixture of cyclic polyphenylene ether ether ketone and linear polyphenylene ether ether ketone is brought into contact with the solvent, but it is preferably performed in a non-oxidizing atmosphere, and inert such as nitrogen, helium, argon, etc. It is preferably carried out in a gas atmosphere, and among these, it is particularly preferred to carry out in a nitrogen atmosphere from the viewpoint of economy and ease of handling.

  The temperature at which the mixture of the cyclic polyphenylene ether ether ketone and the linear polyphenylene ether ether ketone is brought into contact with the solvent is not particularly limited, but generally the higher the temperature, the more the dissolution of the cyclic polyphenylene ether ether ketone in the solvent tends to be promoted. It is in. As described above, since the contact of the mixture of the cyclic polyphenylene ether ether ketone and the linear polyphenylene ether ether ketone with the solvent is preferably carried out under normal pressure, the upper limit temperature is the reflux temperature of the solvent used under atmospheric pressure. In the case of using the above-mentioned preferable solvent, for example, 20 to 150 ° C. can be exemplified as a specific temperature range.

  The time for contacting the mixture of cyclic polyphenylene ether ether ketone and linear polyphenylene ether ether ketone with the solvent cannot be uniquely limited because it varies depending on the type and temperature of the solvent used. For example, 1 minute to 50 hours can be exemplified. In such a range, the cyclic polyphenylene ether ether ketone tends to be sufficiently dissolved in the solvent.

  A method for bringing the mixture into contact with the solvent may be any known general method, and is not particularly limited. For example, a mixture of a cyclic polyphenylene ether ether ketone and a linear polyphenylene ether ether ketone is mixed with the solvent and necessary. Any method may be used, such as a method of recovering the solution portion after stirring according to the method, a method of dissolving the cyclic polyphenylene ether ether ketone in the solvent at the same time as showering the solvent in the above mixture on various filters, or a method based on the Soxhlet extraction method principle. it can. There is no particular limitation on the amount of the solvent used when the mixture of the cyclic polyphenylene ether ether ketone and the linear polyphenylene ether ether ketone is brought into contact with the solvent. For example, the range of 0.5 to 100 can be exemplified by the bath ratio with respect to the weight of the mixture. . When the bath ratio is in such a range, the mixture and the solvent are easily mixed uniformly, and the cyclic polyphenylene ether ether ketone tends to be sufficiently dissolved in the solvent. In general, a larger bath ratio is advantageous for dissolving cyclic polyphenylene ether ether ketone in a solvent, but if it is too large, no further effect can be expected, and conversely an economic disadvantage due to an increase in the amount of solvent used. There is. In addition, when the contact between the mixture and the solvent is repeated, a sufficient effect is often obtained even with a small bath ratio, and the Soxhlet extraction method has a similar effect in principle, so in this case also with a small bath ratio. In many cases, sufficient effects can be obtained.

  After contacting a mixture of cyclic polyphenylene ether ether ketone and linear polyphenylene ether ether ketone with a solvent, a solution in which cyclic polyphenylene ether ether ketone is dissolved is obtained as a solid-liquid slurry containing solid linear polyphenylene ether ether ketone. In this case, it is preferable to recover the solution part using a known solid-liquid separation method. Examples of the solid-liquid separation method include separation by filtration, centrifugation, and decantation. By removing the solvent from the solution thus separated, the cyclic polyphenylene ether ether ketone can be recovered. On the other hand, if the cyclic polyphenylene ether ether ketone still remains for the solid component, it is also possible to obtain the cyclic polyphenylene ether ether ketone in a higher yield by repeatedly contacting with the solvent and collecting the solution again.

  The solvent can be removed from the solution containing the cyclic polyphenylene ether ether ketone obtained as described above to obtain the cyclic polyphenylene ether ether ketone as a solid component. The removal of the solvent can be exemplified by, for example, a method of heating and treating under normal pressure, or removal of the solvent using a membrane. However, from the viewpoint of obtaining cyclic polyphenylene ether ether ketone more efficiently and efficiently. A method of removing the solvent by heating at a pressure lower than the pressure is preferred. The solution containing the cyclic polyphenylene ether ether ketone obtained as described above may contain a solid depending on the temperature. In this case, the solid also belongs to the cyclic polyphenylene ether ether ketone. It is preferable to recover together with a component soluble in the solvent at the time of removal, so that cyclic polyphenylene ether ether ketone can be obtained with high yield. Here, the solvent is preferably removed by at least 50% by weight or more, preferably 70% by weight or more, more preferably 90% by weight or more, and still more preferably 95% by weight or more. Although the temperature at which the solvent is removed by heating depends on the type of the solvent used, it cannot be uniquely limited, but a range of 20 to 150 ° C., preferably 40 to 120 ° C. can be selected. In addition, the pressure for removing the solvent is preferably normal pressure or lower, which makes it possible to remove the solvent at a lower temperature.

(2) Polyphenylene ether ether ketone The polyphenylene ether ether ketone of the present invention is a linear compound represented by the following general formula (II) having paraphenylene ketone and paraphenylene ether as repeating structural units.

  The polyphenylene ether ether ketone of the present invention has a reduced viscosity (η) of 0.6 to 2.5 dL / g. Preferably it is 0.6-2.0 dL / g, More preferably, 0.6-1.8 dL / g can be illustrated. If it is less than 0.6, it is not preferable because a large amount of gas at the time of molding tends to cause corrosion of the mold or the physical properties of the obtained molded product tend to deteriorate. On the other hand, if it is larger than 2.5 dL / g, molding processing such as injection molding becomes difficult, which is not preferable. Here, the reduced viscosity is a value measured by the measuring method described in the section of cyclic polyphenylene ether ether ketone.

  The polyphenylene ether ether ketone in the present invention can be produced by heat-opening polymerization of the cyclic polyphenylene ether ether ketone composition.

  The heating temperature at which the cyclic polyphenylene ether ether ketone composition is converted to polyphenylene ether ether ketone by heat-opening polymerization is preferably equal to or higher than the temperature at which the cyclic polyphenylene ether ether ketone composition melts. There are no particular restrictions as long as the temperature is appropriate. When the heating temperature is lower than the melting temperature of the cyclic polyphenylene ether ether ketone, it takes a long time to obtain the polyphenylene ether ether ketone by the heat ring-opening polymerization, or the polyphenylene ether ether ketone is obtained without the heat ring-opening polymerization proceeding. There is a tendency to become impossible. The temperature at which the cyclic polyphenylene ether ether ketone composition melts is determined by the composition and molecular weight of the cyclic polyphenylene ether ether ketone, the weight fraction of the cyclic polyphenylene ether ether ketone contained in the cyclic polyphenylene ether ether ketone composition, However, it is not possible to uniquely indicate the temperature. However, for example, by analyzing a cyclic polyphenylene ether ether ketone composition with a differential scanning calorimeter, it is possible to grasp the melting temperature. As a minimum of heating temperature, 150 degreeC or more can be illustrated, Preferably it is 180 degreeC or more, More preferably, it is 200 degreeC or more, More preferably, it is 220 degreeC or more. In this temperature range, the cyclic polyphenylene ether ether ketone composition melts and tends to be obtained in a short time. On the other hand, if the temperature of the ring-opening polymerization is too high, crosslinking reaction or decomposition reaction between the cyclic polyphenylene ether ether ketone, between the polyphenylene ether ether ketone produced by heating, between the polyphenylene ether ether ketone and the cyclic polyphenylene ether ether ketone, etc. It is desirable to avoid a temperature at which such undesired side reaction is remarkably generated, because typical unfavorable side reaction tends to occur and the characteristics of the obtained polyphenylene ether ether ketone may be deteriorated. As an upper limit of heating temperature, 500 degrees C or less can be illustrated, Preferably it is 400 degrees C or less, More preferably, it is 360 degrees C or less, More preferably, it is 335 degrees C or less, More preferably, it is 300 degrees C or less. Below this temperature range, adverse effects on the properties of the resulting polyphenylene ether ether ketone due to undesirable side reactions tend to be suppressed. When a known cyclic polyphenylene ether ether ketone is used, since the melting point of the cyclic polyphenylene ether ether ketone is high, the heat ring-opening polymerization requires a long time in the above-mentioned preferable temperature range, or the heat ring-opening polymerization does not proceed and the polyphenylene. While the ether ether ketone tends not to be obtained, the cyclic polyphenylene ether ether ketone composition having the melting point of 270 ° C. or less according to the present invention undergoes efficient ring-opening polymerization in the above preferred temperature range. Polyphenylene ether ether ketone is obtained. In the method for producing polyphenylene ether ether ketone of the present invention, it is possible to carry out heat-opening polymerization at a temperature not higher than the melting point of the obtained polyphenylene ether ether ketone.

  Although the reaction time varies depending on the weight fraction and composition ratio of the cyclic polyphenylene ether ether ketone in the cyclic polyphenylene ether ether ketone composition to be used and the conditions such as the heating temperature and the heating ring-opening polymerization method, it cannot be uniformly defined. It is preferable to set so as not to cause an undesirable side reaction such as a cross-linking reaction, which may be in the range of 0.01 to 100 hours, preferably 0.05 to 20 hours, and more preferably 0.05 to 10 hours. . By setting it as these preferable reaction time, it exists in the tendency which can suppress the bad influence on the characteristic of the polyphenylene ether ether ketone obtained by progress of unfavorable side reactions, such as a crosslinking reaction.

  The method for producing polyphenylene ether ether ketone by heat-opening polymerization of the cyclic polyphenylene ether ether ketone composition of the present invention can be carried out in the absence of a catalyst or in the presence of a catalyst. The catalyst here is not particularly limited as long as it is a compound having an effect of accelerating the heat-opening polymerization reaction of the cyclic polyphenylene ether ether ketone composition in the present invention, and is a photopolymerization initiator, radical polymerization initiator, cationic polymerization. Known catalysts such as an initiator, an anionic polymerization initiator, and a transition metal catalyst can be used, and among these, an anionic polymerization initiator is preferable. Examples of the anionic polymerization initiator include inorganic alkali metal salts or organic alkali metal salts. Examples of the inorganic alkali metal salts include alkali metal halides such as sodium fluoride, potassium fluoride, cesium fluoride, and lithium chloride. Examples of the organic alkali metal salt include sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium tert-butoxide, potassium tert-butoxide and other alkali metal alkoxides, sodium phenoxide, potassium phenoxide, sodium 4-phenoxyphenoxide, potassium 4-phenoxyphenoxide, sodium 4-phenylphenoxide, potassium 4-phenylphenoxide, sodium 4-benzoylphenoxide, potassium Alkali metal phenoxides such as um 4-benzoyl phenoxide, lithium acetate, can be exemplified an alkali metal acetate such as sodium acetate potassium acetate. Further, it is presumed that these anionic polymerization initiators exhibit a catalytic action by nucleophilic attack on the cyclic polyphenylene ether ether ketone composition. Therefore, it is possible to use a compound having a nucleophilic attack ability equivalent to those of these anionic polymerization initiators as a catalyst. Examples of such a compound having a nucleophilic attack ability include a polymer having an anion polymerizable terminal. Can do. These anionic polymerization initiators may be used alone or in combination of two or more. By performing the heat-opening polymerization of the cyclic polyphenylene ether ether ketone composition in the presence of these preferred catalysts, polyphenylene ether ether ketone tends to be obtained in a short time. Specifically, the heating time of the heat-opening polymerization is as follows. Examples include 2 hours or less, 1 hour or less, and 0.5 hour or less.

  The amount of the catalyst used varies depending on the molecular weight of the target polyphenylene ether ether ketone and the type of the catalyst, but is usually the main structural unit of cyclic polyphenylene ether ether ketone, -O-Ph-O-Ph-CO-Ph. -(Wherein Ph represents a paraphenylene unit, O represents an oxygen atom, and CO represents a carbonyl unit) 0.001 to 20 mol%, preferably 0.005 with respect to 1 mol of the repeating unit. ˜15 mol%, more preferably 0.01 to 10 mol%. By adding a catalyst amount in this preferred range, the ring-opening polymerization of the cyclic polyphenylene ether ether ketone composition tends to proceed in a short time.

  Regarding the addition of these catalysts, they may be added as they are, but it is preferable to uniformly disperse them after adding the catalyst to the cyclic polyphenylene ether ether ketone composition. Examples of the uniform dispersion method include a mechanical dispersion method and a dispersion method using a solvent. Specific examples of the mechanical dispersion method include a pulverizer, a stirrer, a mixer, a shaker, and a method using a mortar. Specific examples of the method of dispersing using a solvent include a method in which a cyclic polyphenylene ether ether ketone composition is dissolved or dispersed in an appropriate solvent, a catalyst is added thereto, and then the solvent is removed. In addition, when the catalyst is dispersed, when the catalyst is a solid, more uniform dispersion is possible, so that the average particle size of the polymerization catalyst is preferably 1 mm or less.

  The ring-opening polymerization of the cyclic polyphenylene ether ether ketone composition can be carried out either in a solvent or under a substantially solvent-free condition, but the temperature can be raised in a short time, and the reaction rate However, since it tends to be easy to obtain polyphenylene ether ether ketone in a short time, it is preferably carried out under conditions substantially free of a solvent. Here, the substantially solvent-free condition means that the solvent in the cyclic polyphenylene ether ether ketone composition is 20% by weight or less, preferably 10% by weight or less, and more preferably 5% by weight or less.

  Moreover, as a heating method, it is possible to carry out by a method using a normal polymerization reaction apparatus, in a mold for producing a molded article, or by using an extruder or a melt kneader. Any apparatus having a mechanism can be used without any particular limitation, and known methods such as a batch method and a continuous method can be employed.

  The atmosphere during the ring-opening polymerization of the cyclic polyphenylene ether ether ketone composition is not particularly limited, but is preferably performed in a non-oxidizing atmosphere, and is preferably performed under reduced pressure. Moreover, when it carries out under pressure reduction conditions, it is preferable to make it the pressure reduction conditions after making the atmosphere in a reaction system once non-oxidizing atmosphere. Occurrence of undesirable side reactions such as cross-linking reactions and decomposition reactions between cyclic polyphenylene ether ether ketones, between polyphenylene ether ether ketones produced by ring-opening polymerization, and between polyphenylene ether ether ketones and cyclic polyphenylene ether ether ketones. There is a tendency to be able to suppress. Note that the non-oxidizing atmosphere is an atmosphere in which the oxygen concentration in the gas phase in contact with the cyclic polyphenylene ether ether ketone composition is 5% by volume or less, preferably 2% by volume or less, more preferably an oxygen-free atmosphere, that is, nitrogen, It indicates an atmosphere of an inert gas such as helium or argon, and among these, a nitrogen atmosphere is particularly preferred from the viewpoint of economy and ease of handling. The reduced pressure condition means that the reaction system is lower than the atmospheric pressure, and the upper limit is preferably 50 kPa or less, more preferably 20 kPa or less, and even more preferably 10 kPa or less. An example of the lower limit is 0.1 kPa or more, and 0.2 kPa or more is more preferable. When the decompression condition is at least the preferred lower limit, the cyclic compound having a low molecular weight contained in the cyclic polyphenylene ether ether ketone composition is less likely to be volatilized, while when it is less than the preferred upper limit, undesirable side reactions such as a crosslinking reaction tend not to occur.

(3) Inorganic filler (b) Inorganic filler used in the present invention includes fibrous or non-fibrous (plate-like, scale-like, granular, indefinite shape, crushed product, etc.) fillers, specifically For example, glass fiber, PAN-type or pitch-type carbon fiber, stainless steel fiber, metal fiber such as aluminum fiber or brass fiber, gypsum fiber, ceramic fiber, asbestos fiber, zirconia fiber, alumina fiber, silica fiber, oxidation as fibrous filler Examples include titanium fiber, silicon carbide fiber, rock wool, potassium titanate whisker, barium titanate whisker, barium strontium titanate whisker, aluminum borate whisker, silicon nitride whisker, and zinc oxide whisker. Generally used for resin reinforcement If there is no limitation in particular, it can select and use from a long fiber type, a short fiber type chopped strand, a milled fiber, etc., for example. The filler may be coated or focused with a thermoplastic resin such as an ethylene / vinyl acetate copolymer, a thermosetting resin such as an epoxy resin, a silane compound, a titanate compound, or an aluminum compound.

  Zinc oxide whiskers, mica, talc, kaolin, silica, calcium carbonate, glass beads, glass flakes, glass microballoons, clay, molybdenum disulfide, wollastonite, calcium polyphosphate, graphite, metal powder, metal flakes as non-fibrous filler Examples thereof include metal ribbons, metal oxides (alumina, zinc oxide, titanium oxide, etc.), carbon powder, graphite, carbon flakes, scale-like carbon, and nanocarbon tubes. Moreover, silver, nickel, copper, zinc, aluminum, stainless steel, iron, brass, chromium, tin etc. can be illustrated as a specific example of the metal seed | species of metal powder, metal flakes, and a metal ribbon.

  Also possible for non-fibrous fillers are surface treatment agents such as thermoplastic resins such as ethylene / vinyl acetate copolymers, thermosetting resins such as epoxy resins, silane compounds, titanate compounds, and aluminum compounds. It may be processed.

  In addition, for example, high heat conductive fillers are preferably used for applications requiring high heat dissipation, and specifically, metal powder, metal flakes, metal ribbons, metal fibers, metal oxides (alumina, zinc oxide, etc.) , Carbon powder, graphite, PAN-based or pitch-based carbon fiber, carbon flake, scaly carbon, carbon nanotube, boron nitride, aluminum nitride, silicon nitride, silicon carbide and the like.

  Here, specific examples of the metal species of the metal powder, metal flake, and metal ribbon include silver, nickel, copper, zinc, aluminum, stainless steel, iron, brass, chromium, and tin.

Specific examples of the metal oxide include SnO ₂ (antimony dope), In ₂ O ₃ (antimony dope) and ZnO (aluminum dope), and these include titanate, aluminum and silane. The surface treatment may be performed with the surface treatment agent.

The carbon powder is classified into acetylene black, gas black, oil black, naphthalene black, thermal black, furnace black, lamp black, channel black, roll black, disc black, and the like based on the raw materials and the production method. The carbon powder that can be used in the present invention is not particularly limited in terms of its raw material and production method, and among them, acetylene black and furnace black are particularly preferably used. Further, as the carbon powder, various carbon powders having different characteristics such as particle diameter, surface area, DBP (dibutyl phthalate) oil absorption and ash content are manufactured and commercially available. The carbon powder that can be used in the present invention is not particularly limited with respect to these properties, but from the viewpoint of the balance between strength and electrical conductivity, the average primary particle size is 500 nm or less, particularly 5 to 100 nm, It is preferable that it exists in the range of 10-70 nm. The surface area (BET method) is preferably in the range of 10 m ² / g or more, more preferably 30 m ² / g or more. Further, the DBP oil supply amount is preferably 50 mL / 100 g or more, particularly preferably 100 mL / 100 g or more. Furthermore, it is preferable that the ash content is 0.5% or less, particularly 0.3% or less.

  Such carbon powder may be surface-treated with a surface treatment agent such as titanate, aluminum, and silane. Moreover, it is also possible to use what was granulated in order to improve melt-kneading workability | operativity with resin.

  In the present invention, it is preferable to use two or more fibrous and non-fibrous materials in combination for high balance between strength and fluidity. Specifically, (a) one or more combinations selected from graphite and carbon fiber, glass fiber, potassium titanate whisker, barium titanate whisker, aluminum borate whisker, silicon nitride whisker and zinc oxide whisker, or (b) One or more combinations selected from alumina and carbon fiber, glass fiber, potassium titanate whisker, barium titanate whisker, aluminum borate whisker and silicon nitride whisker, or (c) graphite and carbon fiber, zinc oxide whisker and / or One or more combinations selected from non-fibrous fillers can be mentioned.

  In the present invention, the ratio of (a) polyphenylene ether ether ketone to (b) filler exhibits the characteristics of the filler used, and is blended from the viewpoint of balance with melt processability, (B) 5-50% by volume of polyphenylene ether ether ketone and (b) 95-50% by volume of inorganic filler, preferably (a) polyphenylene ether ether ketone 8 with respect to 100% by volume of the total amount of inorganic filler. -45 volume%, (b) 92-55 volume% inorganic filler, More preferably, (a) 10-40 volume% polyphenylene ether ether ketone, (b) 90-60 volume inorganic filler is preferable.

  Further, when using a fibrous filler and a non-fibrous filler in combination, it is preferable that the non-fibrous filler is more than the fibrous filler in terms of the balance of molding fluidity and mechanical strength, specifically, The amount is preferably 2% by weight or more, more preferably 5% by weight or more.

  In order to improve the fluidity and mechanical strength by reducing the porosity between fillers in the filler (b) inorganic filler used as a feature of the present invention, the particle size is distributed over a wide range. It is preferable that the ratio (D90 / D10) of the 90% cumulative particle size (D90) and the 10% cumulative particle size (D10) obtained from the cumulative particle size distribution curve measured by the laser diffraction method is 10 or more. Is preferable, more preferably 11 or more, and still more preferably 13 or more. Although it does not specifically limit as an upper limit, When productivity etc. are considered, it is 1000 or less.

  Further, in order to maximize the individual filler characteristics, the average particle diameter (D50) of the inorganic filler (b) obtained by the laser beam diffraction method is preferably 1 to 100 μm, more preferably 3 to 80 μm. 4 to 50 μm is preferable.

  The measurement by the laser beam diffraction method is a laser diffraction particle size distribution measuring device (for example, a laser diffraction particle size distribution measuring device SALD-3100 manufactured by Shimadzu Corporation) at a concentration of 100 ppm using a dispersible liquid such as water or a solvent as a dispersion medium. Use to measure.

  In addition, since the present invention is highly filled with fillers, lubricity between inorganic fillers is important, and as a particle size distribution therefor, it is ideal to have a uniform distribution over a wide particle size range, a so-called trapezoidal distribution. However, it is also preferable to have a bimodal particle size distribution such as bimodal and trimodal having two mountain distributions. Furthermore, in the case of multimodality, it is preferable that the peak on the coarse particle side is higher in terms of strength improvement.

  In order to make the filler used in the present invention have such a particle size distribution as described above, for example, two or more fillers having different average particle sizes or particle size distributions are used in combination, or those obtained by fractionation by particle size by sieving or the like are desired. The method of mixing so that it may become particle size distribution of this, the method of using together 2 or more types of fillers from which particle size distribution differs are employable.

  The particle size distribution is indicated by a curve in which the amount of particles (%) in each particle size interval measured by a laser diffraction particle size distribution measuring device is plotted. The cumulative particle size distribution curve is equal to or less than the particle size. It is a curve obtained by accumulating the amount of particles (%), and represents the percentage of the total amount of particles having a specific particle diameter or less.

  In addition, the present invention includes the following (c) fatty acid metal salt, ester compound, amide group-containing compound, epoxy compound, and phosphate ester from the viewpoint of imparting bondability at the filler interface and imparting flow improvement during processing. It is preferable to add at least one selected from Such additives include calcium stearate, magnesium stearate, zinc stearate, barium stearate, aluminum stearate, calcium montanate, magnesium montanate, zinc montanate, barium montanate, aluminum montanate and other fatty acid metals Salts, and derivatives thereof, stearates such as methyl stearate and stearate stearate, myristic esters such as myristyl myristate, montanate esters, methacrylate esters such as behenyl methacrylate, pentaerythritol monostearate, 2 -Cetyl ethylhexanoate, methyl palm fatty acid, methyl laurate, isopropyl myristate, octyldodecyl myristate, butyl stearate, stearic acid -Ethylhexyl, isotridecyl stearate, methyl caprate, methyl myristate, methyl oleate, octyl oleate, lauryl oleate, oleyl oleate, 2-ethylhexyl oleate, decyl oleate, octidodecyl oleate, isobutyl oleate, etc. Monohydric alcohol esters of fatty acids and their derivatives, distearyl phthalate, distearyl trimelliate, dimethyl adipate, dioleyl adipate, adipate, ditridecyl phthalate, diisobutyl adipate, diisodecyl adipate, dibutyl glycol adipate , 2-ethylhexyl phthalate, diisononyl phthalate, didecyl phthalate, tri (2-ethylhexyl) trimellitic acid, triisodecyl trimellitic acid, etc. Fatty acid ester of polybasic acid, stearic acid monoglyceride, palmitic acid / stearic acid monoglyceride, stearic acid mono / diglyceride, stearic acid / oleic acid / mono / diglyceride, fatty acid ester of glycerin such as behenic acid monoglyceride and their derivatives, sorbitan tri Stearate, sorbitan monostearate, sorbitan monostearate, sorbitan distearate, sorbitan monopalmitate, sorbitan monostearate, polyethylene glycol monostearate, polyethylene glycol distearate, polypropylene glycol monostearate, pentaerythritol monostearate Rate, sorbitan monolaurate, sorbitan trioleate, sorbitan monooleate, sorbi Tansesquiolate, sorbitan monolaurate, polyoxymethylene sorbitan monolaurate, polyoxymethylene sorbitan monopalinate, polyoxymethylene sorbitan monostearate, polyoxymethylene sorbitan monooleate, polyoxymethylene sorbitan tetraoleate, polyethylene glycol, Polyethylene glycol monolaurate, polyethylene glycol monooleate, polyoxyethylene bisphenol A lauric acid ester, fatty acid ester of polyhydric alcohol such as pentaerythritol, pentaerythritol monooleate, and derivatives thereof, ethylene bisstearylamide, ethylenebisoleylamide , Amide group-containing compounds such as stearyl erucamide, novolac phenyl type, bisphenol Nord type monofunctional and polyfunctional epoxy compounds, aromatic phosphoric acid esters such as triphenyl phosphate, and phosphate esters such as aromatic condensed phosphate.

  In particular, the phosphoric acid ester is selected from monoesters, diesters, triesters, and tetraesters of phosphoric acid, and preferred examples include those represented by the following formula (III).

  First, the structure of the phosphate ester represented by the formula (III) will be described. In the formula (III), n is an integer of 0 or more, preferably 0 to 10, particularly preferably 0 to 5. The upper limit is preferably 40 or less from the viewpoint of dispersibility.

  K and m are each an integer of 0 or more and 2 or less, and k + m is an integer of 0 or more and 2 or less, preferably k or m is an integer of 0 or more and 1 or less, particularly preferably k or m. Is 1 respectively.

In the formula (III), R ^{3 to} R ¹⁰ represent the same or different hydrogen or an alkyl group having 1 to 5 carbon atoms. Specific examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, tert-pentyl group, Among them, hydrogen, methyl group, and ethyl group are preferable, and hydrogen is particularly preferable.

Ar ¹ , Ar ² , Ar ³ and Ar ⁴ represent the same or different aromatic groups or aromatic groups substituted with an organic residue containing no halogen. Examples of the aromatic group include aromatic groups having a benzene skeleton, a naphthalene skeleton, an indene skeleton, and an anthracene skeleton, and among them, those having a benzene skeleton or a naphthalene skeleton are preferable. These may be substituted with a halogen-free organic residue (preferably an organic residue having 1 to 8 carbon atoms), and the number of substituents is not particularly limited, but may be 1 to 3. preferable. Specific examples include phenyl groups, tolyl groups, xylyl groups, cumenyl groups, mesityl groups, naphthyl groups, indenyl groups, anthryl groups and the like, but phenyl groups, tolyl groups, xylyl groups, cumenyl groups, A naphthyl group is preferable, and a phenyl group, a tolyl group, and a xylyl group are particularly preferable.

Y represents a direct bond, O, S, SO ₂ , C (CH ₃ ) ₂ , CH ₂ , CH (Ph), and Ph represents a phenyl group.

  Specific examples of such phosphate esters are selected from Daihachi Chemical Co., Ltd. PX-200, PX-201, PX-130, CR-733S, TPP, CR-741, CR-747, TCP, TXP, CDP. One or more selected from the group consisting of PX-200, TPP, CR-733S, CR-741, and CR-747, particularly preferably PX-200. , CR-733S and CR-741 can be used, but PX-200 is most preferable.

  In this invention, any 1 type of phosphate ester, or a mixture of 2 or more types may be sufficient. The addition amount of such additives is 0.1 to 10 parts by weight, preferably 0.1 to 8 parts by weight, based on 100 parts by weight of the total amount of (a) thermoplastic resin and (b) inorganic filler. A range of 0.3 to 6 parts by weight is preferably selected.

  (C) When the addition amount of the fatty acid metal salt, ester compound, amide group-containing compound, epoxy compound, and phosphate ester is within the above range, the surface of the molded product obtained is too much in the range of the present invention. The mechanical properties are not deteriorated due to peeling of the interface between (a) polyphenylene ether ether ketone and (b) filler.

  In the highly filled resin composition of the present invention, other components such as antioxidants and heat stabilizers (hindered phenol-based, hydroquinone-based, phosphite-based, and substituted products thereof are used as long as the effects of the present invention are not impaired. Etc.), weathering agents (resorcinol, salicylate, benzotriazole, benzophenone, hindered amine, etc.), mold release agents and lubricants (montanic acid and its metal salts, esters, half esters, stearyl alcohol, stearamide, various Bisamide, bisurea, polyethylene wax, etc.), pigment (cadmium sulfide, phthalocyanine, carbon black for coloring, etc.), dye (nigrosine, etc.), crystal nucleating agent (talc, silica, kaolin, clay, etc.), plasticizer (p-oxy) Octyl benzoate, N-butylbenzenesulfone Antistatic agents (alkyl sulfate type anionic antistatic agents, quaternary ammonium salt type cationic antistatic agents, nonionic antistatic agents such as polyoxyethylene sorbitan monostearate, betaine amphoteric antistatic agents) Agent), flame retardant (eg, red phosphorus, phosphate ester, melamine cyanurate, magnesium hydroxide, aluminum hydroxide, hydroxide, ammonium polyphosphate, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, bromine Epoxy resins or combinations of these brominated flame retardants and antimony trioxide), and other polymers can be added.

(4) Manufacturing Method of Filler Highly Filled Resin Composition The filler highly filled resin composition of the present invention contains a large amount of filler (addition amount is (a) polyphenylene ether ether ketone and (b) total amount of inorganic filler 100 Since (b) the inorganic filler is 95 to 50% by volume with respect to the volume%), it is difficult to produce by an ordinary melt-kneading method. As a method for obtaining a highly filled resin composition in which an inorganic filler exceeding 50% by volume is added, for example, as disclosed in JP-A-8-1663, the head portion of the extruder is removed and extruded, and coarsely pulverized and uniformly blended. The method or the method of compressing and molding the raw material into a tablet can be mentioned. In particular, the method of tableting by compressing the raw material is preferable from the viewpoint of the quality stability of the obtained composition.

  In the present invention, a tablet refers to a granular material obtained by compacting a raw material containing a powdery raw material in a solid phase. Such a tablet can be obtained by compression molding a raw material containing a powdery raw material in a solid phase. Can do. In the above description, the solid phase means that the polyphenylene ether ether ketone component contained in the raw material is not melted. For the compression molding, it is preferable to use a molding machine having a compression roll such as a tableting machine (rotary, single-shot, double, triple) or briquette machine.

As a specific method for tableting, for example, a thermoplastic resin powder and an inorganic filler are uniformly blended in a solid phase using a Banbury mixer, kneader, roll, uniaxial or biaxial extruder, and a tableting machine. Or it can obtain by making into a tablet (tablet) with the molding machine which has a compression roll. Also, polyphenylene ether ether ketone and inorganic filler are dry blended in advance using a Banbury mixer, kneader, or roll, or melt blended once using a single or twin screw extruder, etc. After forming into a powder form, it is also possible to form tablets (tablets) with a tableting machine or a molding machine having a compression roll. In this case, the thermoplastic resin component used for melt kneading is not particularly limited as long as it can be melt kneaded, either in powder form or pellet form, but it is a powder from the viewpoint of reducing variation in characteristics due to poor dispersion of inorganic filler. Preferably, it is in the form of a pulverized product. In addition, when the composition previously melt-kneaded using a single-screw or twin-screw extruder is powdered, if the amount of inorganic filler used is large, the fluidity deteriorates, so the pellet cannot be extruded from the die. However, in this case, as described in JP-A-8-1663, kneading and extrusion can be performed with the head portion of the extruder being opened. When the amount of the inorganic filler is large, a flaky composition may be obtained. In the present invention, if necessary, a pellet or flake composition obtained by melt-kneading in advance by these methods is cooled and pulverized to form a powder and then tableted. In addition, these methods can be combined into tablets. That is, a raw material selected from the following (A) to (D) can be adjusted to have a desired content and tableted.
(A) Polyphenylene ether ether ketone (b) Inorganic filler (c) (c) One or more of fatty acid metal salts, ester compounds, amide group-containing compounds, epoxy compounds, and phosphate esters (d) (a) A composition obtained by melt-kneading two or more components selected from the components (c) and having the component (a) or (b) as essential components, preferably a lump and a powder thereof. In the point that the process is simple, a mixture obtained by uniformly blending the raw materials of the above (a) and (b) and the raw material of (c) in a solid phase state as necessary is obtained by a tableting machine or a molding machine having a compression roll. A method of making a tablet is preferred.

  As the powders of the components (a) and (c), those available in powder form such as polyphenylene ether ether ketone may be used. It can also be obtained by pulverizing the pellets at room temperature or by freeze pulverization. The freeze pulverization can be carried out by using a generally known hammer type pulverizer, cutter type pulverizer, or stone mill type pulverizer after being frozen with dry ice or liquid nitrogen. As the powder of polyphenylene ether ether ketone used in the present invention, in the case of measuring based on the laser diffraction type particle size distribution measurement method from the point of making the composition uniform between the obtained tablets and improving the handleability of the obtained tablets. The number average particle diameter of the maximum major axis of the particles is preferably 1000 μm or less, more preferably 800 μm or less, and even more preferably 500 μm or less. In order to obtain a powder having such a particle size, the powder obtained by pulverization or the like may be appropriately sieved using a sieve having a desired size.

  As the tablet shape of the highly filled resin composition of the present invention, when considering shape retention during transportation and easy crushability during molding, for example, cylindrical shape, elliptical columnar shape, truncated cone shape, spherical shape, elliptical spherical shape, Examples include egg shape, macek shape, disc shape, cubic shape, and prismatic shape. Among these, a cylindrical shape, an elliptical column shape, a truncated cone shape, a spherical shape, an elliptic spherical shape, an egg shape, and a Macek shape are preferable from the viewpoint of measurement stability during processing.

  Further, the tablet size of the tablet is preferably a bottom surface of 15 mm diameter or less × length of 20 mm or less, and the maximum value of the bottom surface diameter or length (height) is preferably less than 15 mm, and the minimum value is 1 mm or more. It is preferable that As for the method of defining the maximum diameter and the minimum diameter with respect to those having a bottom surface that is not circular, when the maximum diameter of the circumscribed circle is specified, the maximum diameter is preferably less than 15 mm, 1 mm or more, more preferably 12 mm. Hereinafter, it is good that it is 1.5 mm or more.

   In addition, in order to keep the shape stable during transportation, the compression fracture strength value (crush strength value) when pressure is applied perpendicularly to the side of the tableting surface of the tablet or the compression surface of the compression roll, Preferably it is 5-100N, More preferably, it is 15-80N. As a method for obtaining a preferable crushing strength value, for example, it is most dependent on the raw material composition. By adding the component (c) or in the tableting process, the raw material is supplied uniformly to the raw material supply pocket, compression High by reducing the number of rotations of the roll and extending the pressurization time of the material on the compression roll, using a feed screw in the hopper, and effective deaeration and pre-compression before roll compression with the screw. Tablet density is obtained and high crushing strength is obtained. The crushing strength value is measured by placing a tablet on a strain gauge such as a load cell, and lowering the indenter at a low speed (preferably 0.1 to 2.0 mm / sec), and straining the tablet at the time of compressive fracture. A method of measuring the pressure indicated by the gauge can be used.

  In addition, the conversion of the above-described (a ′) cyclic polyphenylene ether ether ketone composition into polyphenylene ether ether ketone is performed in the presence of the above-mentioned (b) inorganic filler and, if necessary, the component (c). It is also possible to produce a filled resin composition. Due to the low melting point characteristics of the cyclic polyphenylene ether ether ketone composition, the cyclic polyphenylene ether ether ketone composition after the solid material such as the inorganic filler and the cyclic polyphenylene ether ether ketone composition form good wetting in the above-mentioned molding temperature range. Can be converted to polyphenylene ether ether ketone, whereby a highly filled resin composition with good wetting can be obtained.

  By using such a method, it becomes possible to obtain a resin material highly filled with a filler that could not be achieved conventionally.

  The molding method for molding the highly filled resin composition of the present invention is a three-dimensional molded product by a normal molding method (injection molding, press molding, injection press molding, etc.), gas injection molding, mucell molding method, etc. However, in view of productivity, injection molding or injection press molding is preferably employed. Moreover, when it has a welding part, it is possible to use general welding methods, such as a hot plate, a vibration, an ultrasonic wave, and a laser.

  The molded product thus obtained makes the best use of the characteristics of the inorganic filler to be used and is capable of being melt-molded. For example, high heat dissipation applications, metal replacement applications, ceramic replacement applications, electromagnetic wave shielding applications, high precision parts ( Low dimensional change), useful for high conductivity applications, specifically, various cases, gear cases, LED lamp related parts, connectors, relay cases, switches, variable capacitor cases, optical pickup lens holders, optical pickup slide bases, Various terminal boards, transformers, printed wiring boards, liquid crystal panel frames, power modules and their housings, plastic magnets, semiconductors, liquid crystal display parts, lamp covers for projectors, FDD carriages, FDD chassis, actuators, HDD parts such as chassis Computer related parts Electric / electronic parts represented by: audio equipment such as VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio laser discs (registered trademark), compact discs, digital video discs Houses represented by parts, lighting parts, refrigerator parts, air conditioner parts, office electrical product parts, office computer-related parts, telephone-related parts, facsimile-related parts, printer heads and parts related to printing heads and transfer rolls, Cleaning jigs, motor parts, microscopes, binoculars, cameras, optical instruments such as watches, precision machine related parts; alternator terminals, alternator connectors, IC regulators, light dimmer potentiometer bases, motor core sealing materials, SCHRATER components, power seat gear housings, thermostat bases for air conditioners, air conditioner panel switch boards, horn terminals, electrical component insulation plates, lamp housings, ignition device cases and other automotive / vehicle related parts, personal computer housings, mobile phone housings, etc. A wide range of fields such as housing applications in the information and communication field, other high-dimensional accuracy, electromagnetic shielding properties, barrier plates that require barrier properties such as gas and liquid, applications that require heat and electrical conductivity, outdoor installation equipment Alternatively, it is useful for building members, and is particularly useful for automobile parts, electrical / electronic parts, thermal equipment parts, etc. that are required to be lightweight and have a high degree of freedom in shape, and are eager to replace metals.

  Hereinafter, although an example is given and the present invention is explained in detail, the gist of the present invention is not limited only to the following examples.

[Reference Example 1] Production of cyclic polyphenylene ether ether ketone composition (A-1) In an autoclave equipped with a stirrer, 1.1 kg (5 mol) of 4,4′-difluorobenzophenone, 0.55 kg (5 mol) of hydroquinone, anhydrous potassium carbonate 0.69 kg (5 mol) and 50 L of N-methyl-2-pyrrolidone were charged. The amount of N-methyl-2-pyrrolidone relative to 1.0 mole of benzene ring component in the mixture is 3.33 liters.

  After sealing the reaction vessel under nitrogen gas at room temperature and normal pressure, the temperature was raised from room temperature to 140 ° C., held at 140 ° C. for 1 hour, then heated to 180 ° C. and held at 180 ° C. for 3 hours, and then 250 ° C. The reaction was carried out by maintaining the temperature at 250 ° C. for 2 hours. After completion of the reaction, the reaction mixture was cooled to room temperature.

  About 0.2 g of the obtained reaction mixture was weighed, diluted with about 4.5 g of THF, a THF-insoluble component was separated and removed by filtration to prepare a high performance liquid chromatography analysis sample, and the reaction mixture was analyzed. As a result, it was confirmed that seven consecutive cyclic polyphenylene ether ether ketones having a repetition number m = 2 to 8 were produced, and the yield of the cyclic polyphenylene ether ketone calculated by an absolute calibration curve method with respect to hydroquinone was 18.0%. The weight fraction of cyclic polyphenylene ether ketone with m = 2 is 32%, the weight fraction of m = 3 is 34%, and the weight of m = 4 with respect to the total weight of cyclic polyphenylene ether ketone with the number of repetitions m = 2-8. The fraction was 21%.

  150 kg of a 1% by weight acetic acid aqueous solution was added to 50 kg of the reaction mixture thus obtained, and the mixture was stirred to form a slurry, then heated to 70 ° C. and stirred for 30 minutes. The slurry was filtered through a filter to obtain a solid content. The operation of dispersing the obtained solid content in 50 kg of deionized water, maintaining at 70 ° C. for 30 minutes and filtering to obtain the solid content was repeated three times. The obtained solid was subjected to vacuum drying at 70 ° C. overnight to obtain about 1.3 kg of dry solid.

  Further, 1.3 kg of the dried solid obtained above was subjected to extraction operation at 80 ° C. for 5 hours using 30 kg of chloroform. Chloroform was distilled off from the resulting extract to obtain a solid content. After adding 2.5 kg of chloroform to this solid content, it was added dropwise to 40 kg of methanol. The resulting precipitated component was filtered off and then vacuum dried at 70 ° C. for 3 hours to obtain 0.19 kg of a white solid.

  This white powder was confirmed to be a compound comprising a phenylene ether ketone unit from the absorption spectrum in infrared spectroscopic analysis, mass spectrum analysis (equipment: Hitachi M-1200H) divided into components by high performance liquid chromatography, and MALDI- From the molecular weight information by TOF-MS, it was found that this white powder was a cyclic polyphenylene ether ether ketone composition mainly composed of a mixture of seven kinds of cyclic polyphenylene ether ether ketones having a repeating number m of 2 to 8 in succession.

  Moreover, as a result of analyzing the obtained cyclic polyphenylene ether ether ketone composition, the weight fraction of the cyclic polyphenylene ether ether ketone mixture in the cyclic polyphenylene ether ether ketone composition is 88% and has a melting point of 160 ° C. I understood that. It was also found that the reduced viscosity of the cyclic polyphenylene ether ether ketone composition was less than 0.02 dL / g.

[Reference Example 2] Production of cyclic polyphenylene ether ether ketone composition (A-2) In an autoclave equipped with a stirrer, 2.25 kg (10 mol) of 4,4'-difluorobenzophenone, 1.10 g (10 mol) of hydroquinone, anhydrous carbonic acid 1.38 kg (10 mol) of potassium and 5 L of N-methyl-2-pyrrolidone were charged. The amount of N-methyl-2-pyrrolidone relative to 1.0 mole of the benzene ring component in the mixture is 0.16 liter.

  After sealing the reaction vessel under nitrogen gas at room temperature and normal pressure, the temperature was raised from room temperature to 140 ° C. and held at 140 ° C. for 1 hour, then heated to 180 ° C. and held at 180 ° C. for 3 hours, then 250 ° C. The reaction was carried out by maintaining the temperature at 250 ° C. for 5 hours, but stirring failure occurred at the initial stage of the reaction, and sufficient stirring was difficult. This is presumed to be due to polymer precipitation in the early stage of the reaction.

  Further, the chloroform-soluble component was recovered from the reaction mixture by the method described in Example 1. As a result, the chloroform-soluble component was obtained at a yield of about 0.8% with respect to hydroquinone. As a result of analyzing the obtained chloroform soluble component, it was found that the weight fraction of the cyclic polyphenylene ether ether ketone mixture in the chloroform soluble component was 53% and had a melting point of 210 ° C. The reduced viscosity of the polyphenylene ether ether ketone composition was 0.12 dL / g.

<Melting point of cyclic polyphenylene ether ether ketone composition>
It measured using DSC7 made from Perkin Elmer. Under the following measurement conditions, the crystallization temperature Tc was 1st Run, and the melting point Tm was 2nd Run.
First Run
・ 50 ℃ × 1 minute hold ・ Temperature increase from 50 ℃ to 320 ℃, temperature increase rate 20 ℃ / min ・ 320 ℃ × 1 minute Temperature decrease from hold 320 ℃ to 100 ℃, temperature decrease rate 20 ℃ / min Second Run
・ 100 ° C. × 1 minute Hold 100 ° C. to 320 ° C., heating rate 20 ° C./min (the melting peak temperature at this time is Tm).

[Reference Example 3] Production of polyphenylene ether ether ketone (B-1) 5 mol% of potassium 4-phenylphenoxide was added to the cyclic polyphenylene ether ether ketone composition obtained in Reference Example 1 and the repeating units of polyphenylene ether ether ketone. The mixture was charged into a 1 L autoclave equipped with a stirrer and replaced with nitrogen. The autoclave was heated to 360 ° C. over 1 hour. When the cyclic PPS compound was melted during the temperature increase, rotation of the stirrer was started, and the mixture was melted and heated for 30 minutes with stirring at a rotational speed of 10 rpm. Thereafter, the polymer was taken out in a gut shape from the discharge port by nitrogen pressure, and the gut was pelletized. As a result of infrared spectrum measurement of the obtained product, it was found that it had a polyphenylene ether ether ketone structure. Moreover, the reduced viscosity of this polyphenylene ether ether ketone was 0.71 dL / g.

[Reference Example 4] Production of polyphenylene ether ether ketone (B-2) 5 mol% of potassium 4-phenylphenoxide was added to the cyclic polyphenylene ether ether ketone composition obtained in Reference Example 2 and the repeating units of polyphenylene ether ether ketone. The mixture was charged into a 1 L autoclave equipped with a stirrer and replaced with nitrogen. The autoclave was heated to 360 ° C. over 1 hour. When the cyclic PPS compound was melted during the temperature increase, rotation of the stirrer was started, and the mixture was melted and heated for 30 minutes with stirring at a rotational speed of 10 rpm. Thereafter, the polymer was taken out in a gut shape from the discharge port by nitrogen pressure, and the gut was pelletized. As a result of infrared spectrum measurement of the obtained product, it was found that it had a polyphenylene ether ether ketone structure. Moreover, the reduced viscosity of this polyphenylene ether ether ketone (B-2) was 0.38 dL / g.

[Reference Example 5] Inorganic filler carbon fiber (CF): MLD300 (fibrous filler, fiber diameter 7 μm, manufactured by Toray Industries, Inc.) Average fiber length 150 μm.
Graphite (CFW-1): CFW50A (manufactured by Chuetsu Graphite Co., Ltd.) Average particle size of 48 μm.
Graphite (CFW-2): CFW18A (manufactured by Chuetsu Graphite Co., Ltd.) Average particle diameter of 18 μm.
Alumina (AL-1): EA-10 (manufactured by Sumitomo Chemical Co., Ltd.) Average particle size 17 μm.
Alumina (AL-2): Al-32B (manufactured by Sumitomo Chemical Co., Ltd.) Average particle size of 2.9 μm.

[Reference Example 6] Additive (uses 42 mesh pass through sieve)
HWE: Montanate ester wax “Lico Wax” E (manufactured by Clariant Japan)
PX: PX-200 (Powdered aromatic condensed phosphate ester, CAS No. 139189-30-3, manufactured by Daihachi Chemical Industry Co., Ltd.) Melting point 95 ° C. (uses 42 mesh pass through sieve).

[Examples 1 to 4, Comparative Example 1]
Tsukishima Kikai Rotary Co., Ltd. equipped with an automatic raw material supply feeder by blending the polyphenylene ether ether ketone of Reference Examples 3 to 4, the inorganic filler shown in Reference Example 5 and the additive of Reference Example 6 in the amount shown in Table 2 using a Henschel mixer. By tableting at room temperature using a tableting machine, a 6 mm diameter × 3 mm long cylindrical tablet (tablet resin composition) (maximum value 6 mm, minimum value 3 mm) was obtained. Subsequently, after drying with a hot air dryer at 140 ° C. for 3 hours, the following evaluation was performed.

[Example 5]
The cyclic polyphenylene ether ether ketone composition obtained in Reference Example 1 and 5 mol% of potassium 4-phenylphenoxide based on the repeating units of polyphenylene ether ether ketone were the same as in Example 3 in a 1 L autoclave equipped with a stirrer. A composition was prepared (polyphenylene ether ether ketone: 39% by volume, alumina: 61% by volume) and replaced with nitrogen. The autoclave was heated to 360 ° C. over 1 hour. When the cyclic polyphenylene ether ketone compound was melted during the temperature increase, rotation of the stirrer was started, and the mixture was melted and heated for 30 minutes with stirring at a rotational speed of 10 rpm. Thereafter, the polymer was taken out in a lump by nitrogen pressure and pulverized to obtain a lump that passed through a 3 mmφ mesh. As a result of infrared spectrum measurement of the obtained product, it was found that it had a polyphenylene ether ether ketone structure. The evaluation shown below was performed using the obtained composition B-3. The reduced viscosity of the polyphenylene ether ether ketone obtained by ring-opening polymerization of only the cyclic polyphenylene ether ether ketone composition obtained in Reference Example 1 under the same conditions was 0.78 dL / g.

<Fluidity>
Using the injection molding machine UH1000 (manufactured by Nissei Plastic Industry Co., Ltd.), the minimum pressure that can be filled with a 100 × 100 × 1 mm thick (film gate) corner forming product under the resin temperature and mold temperature conditions shown in Table 2 It was measured.

<Bending strength>
Using an injection molding machine UH1000 (manufactured by Nissei Plastic Industrial Co., Ltd.), a 100 × 100 × 3 mm thick (film gate) square-shaped product is molded at the minimum pressure +5 MPa under the temperature conditions of the resin temperature and mold temperature shown in Table 2. Two sheets were cut from the center in the flow direction to a width of 12.7 mm, and bending strength was measured in accordance with ASTM D790.

<Corrosion of mold>
80 made of precipitation hardened steel (NAK80; manufactured by Daido Special Steel Co., Ltd.) on the movable side of the mold under the temperature conditions of the resin temperature and mold temperature shown in Table 1 using an injection molding machine UH1000 (manufactured by Nissei Plastic Industrial Co., Ltd.). Inserted a metal insert to obtain an 80 × 2 mm thick (film gate) square-shaped product, and observed the surface cloudiness due to gas when 3000 shots were formed. The evaluation was as follows: No change; ○, Corrosion and surface whitening; x.

<Particle size distribution of filler>
The inorganic filler of Reference Example 6 was blended in a Hensial mixer with the same composition as in Examples and Comparative Examples, and about 0.05 g of the obtained inorganic filler was added to 50 cc of water and stirred. Add a few drops of surfactant diluted with 2-3 drops of “My Pet” (made by Kao Co., Ltd.) to the extent that bubbles do not form, disperse with an ultrasonic cleaner, and then laser diffraction produced by Shimadzu Corporation. The particle amount (%) in each particle diameter section is plotted using the formula particle size distribution analyzer SALD-3100, and from the accumulated distribution curve, D10 (10% portion of the total particle size distribution: small diameter), D50 (average) Particle size), D90 (90% portion of the total particle size distribution: large particle size).

  As is apparent from the results in Table 2, the highly filled resin composition of the present invention is a cyclic polyphenylene ether ether having a reduced viscosity of 0.6 to 2.5 dL / g and containing 60% by weight or more of cyclic polyphenylene ether ether ketone. By using polyphenylene ether ether ketone obtained by ring-opening polymerization of the ketone composition, it is possible to obtain a highly filled filler composition having an excellent balance between molding processability and physical properties. This is presumably due to the fact that the polyphenylene ether ether ketone obtained by ring-opening polymerization is more homogeneous than that obtained by the conventional production method. In particular, it can be seen that characteristics similar to those of fillers used in thermoplastic resins that have not been obtained in the past can be obtained, and the strength that is a problem of high filler filling is improved. In addition, since the corrosiveness of molds, which was a problem during continuous production, can be improved, it will be expanded to automotive parts, electrical / electronic parts, thermal equipment parts, etc. where metal replacement is eagerly desired for weight reduction. It becomes possible.

Claims (9)

The total viscosity of (a) and (b) is 100% by volume, and (a) the reduced viscosity measured under conditions of 98% by weight sulfuric acid at a concentration of 0.1 g / dL and 25 ° C. is 0.6 to 2.5 dL / g. The filler high filling resin composition which mix | blends polyphenylene ether ether ketone 5-50 volume% which exists in the range of (b), and (b) 95-50 volume% of inorganic fillers. The said polyphenylene ether ether ketone is obtained by carrying out ring-opening polymerization of the composition containing 60 weight% or more of cyclic polyphenylene ether ether ketone represented by the following general formula (I). Filler highly filled resin composition.

(M is an integer of 2 to 40, and a mixture of compounds in which m is any of 2 to 40 may be used.) (B) A ratio (D90 / D10) of 90% cumulative particle size (D90) and 10% cumulative particle size (D10) obtained from the cumulative particle size distribution curve of the inorganic filler is 10 or more. Or the filler high filling resin composition in any one of 2. Furthermore, (c) one or more of fatty acid metal salts, ester compounds, amide group-containing compounds, epoxy compounds, and phosphate esters are added to 100 parts by weight of the total amount of (a) and (b). The filler high-filling resin composition according to any one of claims 1 to 3, comprising 5 to 10 parts by weight. A method for producing a tablet comprising a highly filled filler resin composition, wherein the highly filled resin composition according to any one of claims 1 to 4 is compressed into a tablet in a solid state. The tablet which compression-molded the filler high filling resin composition in any one of Claims 1-4 in a solid-phase state. A molded article formed by injection molding the highly filled resin composition according to any one of claims 1 to 4 or the tablet according to claim 6. Cyclic polyphenylene ether ether ketone composition 5 containing (a ′) 60% by weight or more of cyclic polyphenylene ether ether ketone represented by the following general formula (I), wherein the total of (a ′) and (b) is 100% by volume: A method for producing a highly-filled filler resin composition, comprising blending ˜50 vol% and (b) 95-50 vol% inorganic filler, followed by ring-opening polymerization in the presence of a catalyst or an initiator.

(M is an integer of 2 to 40, and a mixture of compounds in which m is any of 2 to 40 may be used.) (B) The ratio (D90 / D10) of the 90% cumulative particle size (D90) and the 10% cumulative particle size (D10) obtained from the cumulative particle size distribution curve of the inorganic filler is 10 or more. A method for producing a highly filled resin composition according to claim 1.