Particles, composition, molded body, and method for producing particles

Abstract

To provide: particles in which a filler is sufficiently dispersed in a resin; a composition; a molded body; and a method for producing particles.SOLUTION: Particles each containing a super engineering plastic resin, a filler, and a compound (I) having a plurality of groups (I) represented by the following formula, wherein the super engineering plastic resin and the filler are bonded by the intermediary of the compound (I). (In the formula, R1 and R2 are the same or different, are each a hydrogen atom or an organic group, and may be bonded to each other to form a ring structure. A double line expressed by a solid line and a broken line represents a single bond or a double bond.)SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to particles, compositions, compacts, and methods for producing particles. [Background technology]

[0002] Various studies are being conducted on methods for improving the physical properties of composite materials containing fillers and resins. For example, Patent Document 1 describes that a fluororesin composition with excellent electrical properties can be obtained by blending a fluororesin with carbon nanotubes that have been surface-treated with a fluorine-based surfactant. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-146081 Summary of the Invention [Problem to be solved by the invention]

[0004] However, fillers usually have a high tendency to aggregate, and therefore, it may not be possible to sufficiently disperse the fillers in the resin.

[0005] An object of the present disclosure is to provide particles in which a filler is sufficiently dispersed in a resin, a composition, a molded body, and a method for producing the particles. [Means for solving the problem]

[0006] The present disclosure (1) is a particle comprising a super engineering plastic resin, a filler, and a compound (I) having a plurality of groups (I) represented by the following formula, wherein the super engineering plastic resin and the filler are bonded via the compound (I). [ka] (In the formula, R 1 and R2 are the same or different and represent hydrogen or an organic group, and may be bonded to each other to form a ring structure. A double line represented by a solid line and a dashed line represents a single bond or a double bond.

[0007] The present disclosure (2) is the particle according to the present disclosure (1), wherein the super engineering plastic resin has a thermal decomposition temperature of 330° C. or higher.

[0008] The present disclosure (3) is the particle according to the present disclosure (1) or (2), wherein the super engineering plastic resin has a continuous use temperature of 140°C or higher.

[0009] The present disclosure (4) is a particle according to any one of the present disclosures (1) to (3), wherein the super engineering plastic resin is at least one selected from the group consisting of fluororesin, liquid crystal polymer, polyetherimide, polyphenylene sulfide, polyaryletherketone, polysulfone, and polyethersulfone.

[0010] The present disclosure (5) is a particle according to any one of the present disclosures (1) to (4), wherein the super engineering plastic resin is at least one selected from the group consisting of fluororesin, liquid crystal polymer, polyaryl ether ketone, and polyether sulfone.

[0011] The present disclosure (6) is the particle according to any one of the present disclosures (1) to (5), in which the super engineering plastic resin is a perfluororesin.

[0012] The present disclosure (7) is a particle according to any one of the present disclosures (1) to (6), wherein the super engineering plastic resin is at least one selected from the group consisting of polytetrafluoroethylene, tetrafluoroethylene / perfluoro(alkyl vinyl ether) copolymer, and tetrafluoroethylene / hexafluoropropylene copolymer.

[0013] The present disclosure (8) is a particle according to any one of the present disclosures (1) to (7), wherein the super engineering plastic resin is at least one selected from the group consisting of a tetrafluoroethylene / perfluoro(alkyl vinyl ether) copolymer and a tetrafluoroethylene / hexafluoropropylene copolymer.

[0014] The present disclosure (9) is the particle according to any one of the present disclosures (1) to (8), wherein the filler is a nanofiller.

[0015] The present disclosure (10) is the particle according to any one of the present disclosures (1) to (9), wherein the filler is a carbon nanotube.

[0016] The present disclosure (11) is the particle according to any one of the present disclosures (1) to (10), wherein the filler is at least one selected from the group consisting of multi-walled carbon nanotubes and single-walled carbon nanotubes.

[0017] The present disclosure (12) is the particle according to any one of the present disclosures (1) to (11), in which the content of the filler is 0.001 to 30% by mass.

[0018] The present disclosure (13) is the particle according to any one of the present disclosures (1) to (12), wherein the group (I) is an oxazoline group and the compound (I) is an oxazoline compound.

[0019] The present disclosure (14) is the particle according to the present disclosure (13), wherein the oxazoline compound is an oxazoline group-containing polymer.

[0020] The present disclosure (15) is the particle according to the present disclosure (14), wherein the molecular weight of the oxazoline group-containing polymer is 2,000 to 400,000.

[0021] The present disclosure (16) is the particle according to the present disclosure (14) or (15), wherein the oxazoline group-containing polymer contains at least one repeating unit selected from the group consisting of a repeating unit derived from 2-vinyl-2-oxazoline and a repeating unit derived from 2-isopropenyl-2-oxazoline.

[0022] The present disclosure (17) is the particle according to any one of the present disclosures (14) to (16), in which the oxazoline group-containing polymer is poly-2-vinyl-2-oxazoline.

[0023] The present disclosure (18) is the particle according to any one of the present disclosures (14) to (16), in which the oxazoline group-containing polymer is a copolymer of 2-isopropenyl-2-oxazoline and an acrylic monomer.

[0024] The present disclosure (19) is the particle according to any one of the present disclosures (1) to (18), in which the content of the compound (I) is 0.01 to 50 mass %.

[0025] The present disclosure (20) is the particle according to any one of the present disclosures (1) to (19), wherein the content of the super engineering plastic resin is 80 to 99.9% by mass, the content of the filler is 0.01 to 0.5% by mass, and the content of the compound (I) is 0.1 to 10% by mass.

[0026] The present disclosure (21) is a composition containing the particles according to any one of the present disclosures (1) to (20).

[0027] The present disclosure (22) is the composition according to the present disclosure (21), which is solid or liquid at 25°C.

[0028] The present disclosure (23) is a molded article using the composition according to the present disclosure (21) or (22).

[0029] This disclosure (24) has a volume resistivity of 1.0 × 10 10 The molded article according to the present disclosure (23) has a resistivity of Ω·cm or less.

[0030] In the present disclosure (25), in image analysis by optical microscope observation, aggregates with a width of 50 μm or more were found to be 0.3 mm 2 The molded article according to the present disclosure (23) or (24), wherein the number of particles per area is 20 or less.

[0031] The present disclosure (26) is a method for producing particles, comprising: step 1 of mixing component A with compound (I) having a plurality of groups (I) represented by the following formula; step 2 of mixing the mixture obtained in step 1 with component B in the presence of a solvent; and step 3 of collecting particles from the dispersion obtained in step 2, wherein component A contains one of a super engineering plastic resin and a filler, and component B contains the other. [ka] (In the formula, R 1 and R 2 are the same or different and represent hydrogen or an organic group, and may be bonded to each other to form a ring structure. A double line represented by a solid line and a dashed line represents a single bond or a double bond.

[0032] The present disclosure (27) is the method for producing particles according to the present disclosure (26), in which in the step 1, the component A and the compound (I) are mixed in the presence of a solvent.

[0033] The present disclosure (28) is the method for producing particles according to the present disclosure (26) or (27), wherein in the step 2, the component A conjugated with the compound (I) and the component B are mixed in the presence of a solvent.

[0034] The present disclosure (29) is the method for producing particles according to any one of the present disclosures (26) to (28), wherein in the step 3, the particles are collected from the dispersion liquid obtained in the step 2 by centrifugation. [Effects of the Invention]

[0035] According to the present disclosure, it is possible to provide particles in which a filler is sufficiently dispersed in a resin, a composition, a molded body, and a method for producing the particles. [Brief explanation of the drawings]

[0036] [Figure 1] 1 is a micrograph showing the dispersion state of Example 1. [Figure 2] 1 is a micrograph showing the dispersion state of Example 2. [Figure 3] 1 is a micrograph showing the dispersion state of Comparative Example 1. [Figure 4] 1 is a micrograph showing the dispersion state of Example 3. [Figure 5] 1 is a micrograph showing the dispersion state of Example 4. [Figure 6] 1 is a micrograph showing the dispersion state of Example 5. DETAILED DESCRIPTION OF THE INVENTION

[0037] As used herein, "organic group" means a group containing one or more carbon atoms or a group formed by removing one hydrogen atom from an organic compound. Examples of the "organic group" are: an alkyl group optionally having one or more substituents; an alkenyl group optionally having one or more substituents; an alkynyl group optionally having one or more substituents; a cycloalkyl group optionally having one or more substituents; a cycloalkenyl group optionally having one or more substituents, a cycloalkadienyl group optionally having one or more substituents, an aryl group optionally having one or more substituents; an aralkyl group optionally having one or more substituents; a non-aromatic heterocyclic group optionally having one or more substituents, a heteroaryl group optionally having one or more substituents; cyano group, formyl group, RaO-, RaCO-, RaSO2-, RaCOO-, RaNRaCO-, RaCONRa-, RaOCO-, RaOSO2- and, RaNRbSO2- (In these formulas, Ra independently represents: an alkyl group optionally having one or more substituents; an alkenyl group optionally having one or more substituents; an alkynyl group optionally having one or more substituents; a cycloalkyl group optionally having one or more substituents; a cycloalkenyl group optionally having one or more substituents, a cycloalkadienyl group optionally having one or more substituents, an aryl group optionally having one or more substituents; an aralkyl group optionally having one or more substituents; a non-aromatic heterocyclic group optionally having one or more substituents, or a heteroaryl group optionally having one or more substituents; Rb is independently H or an alkyl group which may have one or more substituents. Includes. The organic group is preferably an alkyl group which may have one or more substituents.

[0038] The present disclosure will be specifically described below.

[0039] <Particle> The particles of the present disclosure include a super engineering plastic resin, a filler, and a compound (I) having a plurality of groups (I) represented by the following formula, and the super engineering plastic resin and the filler are bonded via the compound (I). [ka] (In the formula, R 1 and R 2are the same or different and represent hydrogen or an organic group, and may be bonded to each other to form a ring structure. A double line represented by a solid line and a dashed line represents a single bond or a double bond.

[0040] According to the particles of the present disclosure, the super engineering plastic resin and the filler are bonded via Compound (I), resulting in a structure in which the super engineering plastic resin is coated with the filler. This suppresses filler aggregation and allows the filler to be sufficiently dispersed in the super engineering plastic resin. As a result, even a small amount of filler can change the physical properties of the resin. For example, if the filler is a conductive filler, it can impart conductivity to the resin.

[0041] The thermal decomposition temperature of the super engineering plastic resin is preferably 330°C or higher, more preferably 350°C or higher, even more preferably 370°C or higher, and is preferably 560°C or lower, more preferably 540°C or lower, even more preferably 520°C or lower. The thermal decomposition temperature of super engineering plastic resin was measured using a thermal analyzer, STA7200, manufactured by Hitachi High-Tech Science Corporation. Measurements were performed under a nitrogen purge atmosphere at 200 mL / min. 10 mg of sample was placed in an aluminum pan, held at 25°C for 10 minutes, and then heated to 600°C at a rate of 10°C / min. The temperature at which the mass decreased by 5% from the initial mass (Td5) was taken as the thermal decomposition temperature.

[0042] The continuous use temperature of the super engineering plastic resin is preferably 140° C. or higher, more preferably 160° C. or higher, and even more preferably 170° C. or higher. There is no particular upper limit, and the higher the temperature the better, but it may be, for example, 260° C. In this specification, the continuous use temperature is the temperature at which the physical property value deteriorates by 50% from the initial value when left in the atmosphere at a constant temperature for 40,000 hours, and is measured in accordance with UL746B.

[0043] The super engineering plastic resin is preferably at least one selected from the group consisting of fluororesin, liquid crystal polymer, polyetherimide, polyphenylene sulfide, polyaryl ether ketone, polysulfone, and polyethersulfone, more preferably at least one selected from the group consisting of fluororesin, liquid crystal polymer, polyaryl ether ketone, and polyethersulfone, and even more preferably fluororesin.

[0044] Examples of fluororesins include polytetrafluoroethylene [PTFE], tetrafluoroethylene [TFE] / perfluoro(alkyl vinyl ether) [PAVE] copolymer [PFA], TFE / hexafluoropropylene [HFP] copolymer [FEP], ethylene [Et] / TFE copolymer [ETFE], Et / TFE / HFP copolymer [EFEP], polychlorotrifluoroethylene [PCTFE], chlorotrifluoroethylene [CTFE] / TFE copolymer, CTFE / TFE / PAVE copolymer, and Et / CTFE copolymer.

[0045] The fluororesin is preferably a perfluororesin, more preferably at least one selected from the group consisting of polytetrafluoroethylene [PTFE], tetrafluoroethylene [TFE] / perfluoro(alkyl vinyl ether) [PAVE] copolymer [PFA], and tetrafluoroethylene [TFE] / hexafluoropropylene [HFP] copolymer [FEP], further preferably at least one selected from the group consisting of PFA and FEP, and particularly preferably FEP.

[0046] The PTFE may be a TFE homopolymer consisting of only tetrafluoroethylene (TFE) units, or may be a modified PTFE containing TFE units and modified monomer units based on a modified monomer copolymerizable with TFE.

[0047] The modifying monomer is not particularly limited as long as it is copolymerizable with TFE, and examples thereof include perfluoroolefins such as hexafluoropropylene [HFP], chlorofluoroolefins such as chlorotrifluoroethylene [CTFE], hydrogen-containing fluoroolefins such as trifluoroethylene and vinylidene fluoride [VdF], perfluorovinyl ethers, perfluoroalkyl allyl ethers, (perfluoroalkyl)ethylenes, ethylene, etc. The modifying monomer used may be one type or multiple types.

[0048] The perfluorovinyl ether is not particularly limited, and examples thereof include perfluorovinyl ethers represented by the following general formula (1): CF2=CF-ORf (1) (wherein Rf represents a perfluoroorganic group). In this specification, the "perfluoroorganic group" refers to an organic group in which all hydrogen atoms bonded to carbon atoms are substituted with fluorine atoms. The perfluoroorganic group may have an ether oxygen.

[0049] An example of the perfluorovinyl ether is perfluoro(alkyl vinyl ether) [PAVE], which is represented by the general formula (1) in which Rf represents a perfluoroalkyl group having 1 to 10 carbon atoms. The number of carbon atoms in the perfluoroalkyl group is preferably 1 to 5.

[0050] Examples of the perfluoroalkyl group in PAVE include perfluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, and perfluorohexyl group, but perfluoro(propyl vinyl ether) [PPVE], in which the perfluoroalkyl group is a perfluoropropyl group, is preferred.

[0051] Further, the perfluorovinyl ether includes those represented by the general formula (1) in which Rf is a perfluoro(alkoxyalkyl) group having 4 to 9 carbon atoms, and those represented by the following formula:

[0052] [ka]

[0053] (wherein m represents 0 or an integer of 1 to 4), and Rf is a group represented by the following formula:

[0054] [ka]

[0055] (wherein n represents an integer of 1 to 4).

[0056] The (perfluoroalkyl)ethylene is not particularly limited, and examples thereof include (perfluorobutyl)ethylene [PFBE], (perfluorohexyl)ethylene [PFHE], and (perfluorooctyl)ethylene.

[0057] The modifying monomer in the modified PTFE is preferably at least one selected from the group consisting of HFP, CTFE, VdF, PPVE, PFBE, and ethylene, and more preferably at least one selected from the group consisting of HFP and CTFE.

[0058] In the modified PTFE, the content of the modifying monomer unit is preferably in the range of 0.00001 to 1.0% by mass. The lower limit of the content of the modifying monomer unit is more preferably 0.0001% by mass, even more preferably 0.001% by mass, even more preferably 0.005% by mass, especially preferably 0.010% by mass, and particularly preferably 0.030% by mass. The upper limit of the content of the modifying monomer unit is preferably 0.90% by mass, more preferably 0.50% by mass, even more preferably 0.40% by mass, and even more preferably 0.30% by mass. In this specification, the modified monomer unit means a part of the molecular structure of the modified PTFE that is derived from the modified monomer.

[0059] The melting point of PTFE is preferably 324 to 360°C. The melting point of PTFE refers to the first melting point. The first melting point is the temperature corresponding to the maximum value on the heat of fusion curve when PTFE that has not been heated to a temperature of 300°C or higher is heated at a rate of 10°C / min using a differential scanning calorimeter (DSC).

[0060] The standard specific gravity (SSG) of PTFE is preferably 2.130 to 2.280. The standard specific gravity is more preferably 2.220 or less, and even more preferably 2.200 or less. It is also preferably 2.140 or more, and even more preferably 2.150 or more. The SSG is measured by the water displacement method in accordance with ASTM D-792 using a sample molded in accordance with ASTM D 4895-89.

[0061] The PTFE preferably has non-melt-fabricability, which means that the melt flow rate cannot be measured at a temperature higher than the crystallization melting point in accordance with ASTM D-1238 and D-2116.

[0062] Although the PFA is not particularly limited, a copolymer having a molar ratio of TFE units to PAVE units (TFE units / PAVE units) of 70 / 30 or more and less than 99 / 1 is preferred. A more preferred molar ratio is 70 / 30 or more and 98.9 / 1.1 or less, and an even more preferred molar ratio is 80 / 20 or more and 98.9 / 1.1 or less. The PFA preferably contains 0.1 to 10 mol % of monomer units derived from a monomer copolymerizable with TFE and PAVE (a copolymer having a total of 90 to 99.9 mol % of TFE units and PAVE units), more preferably 0.1 to 5 mol %, and particularly preferably 0.2 to 4 mol %.

[0063] Examples of the monomer copolymerizable with TFE and PAVE include HFP, a copolymer of the formula (I): CZ 1 Z 2 =CZ 3 (CF2) n Z 4 (In the formula, Z 1 , Z 2and Z 3 are the same or different and represent a hydrogen atom or a fluorine atom; Z 4 represents a hydrogen atom, a fluorine atom or a chlorine atom, and n represents an integer of 2 to 10.) and a vinyl monomer represented by formula (II): CF2=CF-OCH2-Rf 1 (In the formula, Rf 1 represents a perfluoroalkyl group having 1 to 5 carbon atoms, an alkyl perfluorovinyl ether derivative represented by the formula (X): CZ 5 Z 6 =CZ 7 -CZ 8 Z 9 -O-Rf 4 (in the formula, in the formula, Z 5 , Z 6 and Z 7 are the same or different and represent a hydrogen atom, a chlorine atom or a fluorine atom; Z 8 and Z 9 represents a hydrogen atom or a fluorine atom, and Rf 4 represents a perfluoroalkyl group having 1 to 5 carbon atoms. Examples of the allyl ether monomer include an allyl ether monomer represented by CH2=CFCF2-O-Rf 4 , CF2=CFCF2-O-Rf 4 (Perfluoroalkyl allyl ether), CF2=CFCH2-O-Rf 4 , CH2=CHCF2-O-Rf 4 (In the formula, Rf 4 is the same as the above formula (X). Further examples of monomers copolymerizable with TFE and PAVE include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and acid anhydrides of unsaturated dicarboxylic acids, such as itaconic acid, itaconic anhydride, citraconic anhydride, and 5-norbornene-2,3-dicarboxylic anhydride.

[0064] The melting point of PFA is preferably from 180 to less than 324°C, more preferably from 230 to 320°C, and even more preferably from 280 to 320°C. The melting point of PFA is the temperature corresponding to the maximum value on the heat of fusion curve when the temperature is increased at a rate of 10°C / min using a differential scanning calorimeter (DSC).

[0065] Although the FEP is not particularly limited, a copolymer having a molar ratio of TFE units to HFP units (TFE units / HFP units) of 70 / 30 or more and less than 99 / 1 is preferred. A more preferred molar ratio is 70 / 30 or more and 98.9 / 1.1 or less, and an even more preferred molar ratio is 80 / 20 or more and 98.9 / 1.1 or less. The FEP preferably contains 0.1 to 10 mol % of monomer units derived from a monomer copolymerizable with TFE and HFP (a copolymer having a total of 90 to 99.9 mol % of TFE units and HFP units), more preferably 0.1 to 5 mol %, and particularly preferably 0.2 to 4 mol %.

[0066] Examples of the monomer copolymerizable with TFE and HFP include PAVE, a monomer represented by formula (X), an alkyl perfluorovinyl ether derivative represented by formula (II), etc. Further examples of the monomer copolymerizable with TFE and HFP include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and acid anhydrides of unsaturated dicarboxylic acids, such as itaconic acid, itaconic anhydride, citraconic anhydride, and 5-norbornene-2,3-dicarboxylic anhydride.

[0067] The melting point of FEP is preferably from 150 to less than 324°C, more preferably from 200 to 320°C, and even more preferably from 240 to 320°C. The melting point of FEP is the temperature corresponding to the maximum value on the heat of fusion curve when the temperature is increased at a rate of 10°C / min using a differential scanning calorimeter (DSC).

[0068] The ETFE is preferably a copolymer having a molar ratio of TFE units to ethylene units (TFE units / ethylene units) of 20 / 80 or more and 90 / 10 or less. A more preferred molar ratio is 37 / 63 or more and 85 / 15 or less, and an even more preferred molar ratio is 38 / 62 or more and 80 / 20 or less. The ETFE may be a copolymer consisting of TFE, ethylene, and a monomer copolymerizable with TFE and ethylene. The ETFE preferably contains 0.1 to 10 mol % of monomer units derived from TFE and a monomer copolymerizable with ethylene (a copolymer having a total of 90 to 99.9 mol % of TFE units and ethylene units), more preferably 0.1 to 5 mol %, and particularly preferably 0.2 to 4 mol %.

[0069] The monomer copolymerizable with TFE and ethylene is represented by the following formula: CH2=CX 1 Rf 2 , CF2=CFRf 2 , CF2=CFORf 2 , CH2=C(Rf 2 )2(where, X 1 is a hydrogen atom or a fluorine atom, Rf 2 represents a fluoroalkyl group which may contain an ether bond.) and a monomer represented by formula (X), among which CF2=CFRf 2 , CF2=CFORf 2 and CH2=CX 1 Rf 2 and a monomer represented by the formula (X), and HFP, CF2=CF-ORf 3 (In the formula, Rf 3 represents a perfluoroalkyl group having 1 to 5 carbon atoms.) 4 (In the formula, Rf 4 represents a perfluoroalkyl group having 1 to 5 carbon atoms. 2 is a fluoroalkyl group having 1 to 8 carbon atoms, CH2=CX 1 Rf 2Further preferred are fluorine-containing vinyl monomers represented by the following formula: Furthermore, examples of the monomer copolymerizable with TFE and ethylene also include unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and acid anhydrides of unsaturated dicarboxylic acids, such as itaconic acid, itaconic anhydride, citraconic anhydride, and 5-norbornene-2,3-dicarboxylic anhydride.

[0070] The melting point of ETFE is preferably from 140 to less than 324°C, more preferably from 160 to 320°C, and even more preferably from 195 to 320°C. The melting point of ETFE is the temperature corresponding to the maximum value on the heat of fusion curve when the temperature is increased at a rate of 10°C / min using a differential scanning calorimeter (DSC).

[0071] The content of each monomer unit in the above-mentioned polymer can be calculated by appropriately combining NMR, FT-IR, elemental analysis, and X-ray fluorescence analysis depending on the type of monomer.

[0072] Fluorine resin has a main chain of 10 carbon atoms. 6 Each of these may have 100 to 2000 unstable terminal groups. Typical unstable terminal groups include -COF and -COOH, and the above number is the total number of these.

[0073] The number of unstable terminal groups can be measured by infrared spectroscopy. Specifically, first, the fluororesin is melt-extruded to produce a film with a thickness of 0.25 to 0.3 mm. This film is analyzed by Fourier transform infrared spectroscopy to obtain an infrared absorption spectrum of the fluororesin, and a difference spectrum is obtained from the base spectrum, which is completely fluorinated and has no unstable terminal groups. From the absorption peaks of specific unstable terminal groups that appear in this difference spectrum, the number of carbon atoms in the fluororesin can be determined according to the following formula (A): 6 The number of unstable terminal groups per unit, N, is calculated. N=I×K / t (A) I: Absorbance K: Correction coefficient t: film thickness (mm)

[0074] The liquid crystal polymer is not particularly limited, but may be a polymer having a liquid crystallization temperature (i.e., melting point) of 180°C to 380°C, and is preferably a thermotropic liquid crystal polymer that changes to a liquid crystal state such as a nematic state upon heating, for example: Type I liquid crystal polymer (biphenol / benzoic acid / parahydroxybenzoic acid (POB) copolymer, etc.) Type II liquid crystal polymers (hydroxynaphthoic acid (HNA) / POB copolymers, etc.) Type III liquid crystal polymer (POB / ethylene terephthalate copolymer, etc.) Among these, from the viewpoints of the kneading temperature and the liquid crystal transition temperature, at least one selected from the group consisting of type I liquid crystal polymers and type II liquid crystal polymers is preferred, and type II liquid crystal polymers are more preferred.

[0075] The melting point of the liquid crystal polymer is preferably 280°C or higher, more preferably 310°C or higher, and is preferably 380°C or lower, more preferably 350°C or lower.

[0076] As the polyetherimide, for example, one having an imide bond and an ether bond in the molecule can be used.

[0077] The glass transition temperature of the polyetherimide is preferably 180°C or higher, more preferably 200°C or higher, and is preferably 300°C or lower, more preferably 280°C or lower.

[0078] As the polyphenylene sulfide, for example, a resin having a structural unit represented by the following formula can be used: The proportion of this structural unit is preferably 70 mol % or more. -(Ph-S)- In the formula, Ph is a phenylene group, and examples of the phenylene group include p-phenylene, m-phenylene, o-phenylene, alkyl-substituted phenylene, phenyl-substituted phenylene, halogen-substituted phenylene, amino-substituted phenylene, amido-substituted phenylene, p,p'-diphenylene sulfone, p,p'-biphenylene, p,p'-biphenylene ether, etc. Among these, p-phenylene is preferred.

[0079] The melting point of polyphenylene sulfide is preferably 240°C or higher, more preferably 270°C or higher, and is preferably 380°C or lower, more preferably 350°C or lower.

[0080] Examples of polyaryletherketone include polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), etc. Among these, PEEK is preferred.

[0081] The melting point of the polyaryletherketone is preferably 320°C or higher, more preferably 340°C or higher, and is preferably 400°C or lower, more preferably 380°C or lower.

[0082] The polysulfone is not particularly limited, and a general polysulfone can be used.

[0083] The glass transition temperature of the polysulfone is preferably 180°C or higher, more preferably 200°C or higher, and even more preferably 220°C or higher, and is preferably 300°C or lower, more preferably 280°C or lower, and even more preferably 260°C or lower.

[0084] The polyethersulfone is not particularly limited, and a general polyethersulfone can be used.

[0085] The glass transition temperature of the polyethersulfone is preferably 180°C or higher, more preferably 200°C or higher, and even more preferably 220°C or higher, and is preferably 300°C or lower, more preferably 280°C or lower, and even more preferably 260°C or lower.

[0086] The melting points of liquid crystal polymers, polyetherimides, polyphenylene sulfides, and polyaryletherketones are the temperatures corresponding to the maximum values ​​on the heat of fusion curves when the temperature is increased at a rate of 10°C / min using a differential scanning calorimeter (DSC). The glass transition temperatures of polyetherimide, polysulfone, and polyethersulfone can be determined by obtaining a DSC curve using a differential scanning calorimeter (Mettler-Toledo, DSC822e) by heating 10 mg of a sample at a rate of 10°C / min, and by determining the temperature at the midpoint between the two intersections of the extension of the baseline before and after the second-order transition of the DSC curve and the tangent to the inflection point of the DSC curve.

[0087] In the particles of the present disclosure, the content of the super engineering plastic resin is preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and is preferably 99.999% by mass or less, more preferably 99.99% by mass or less, even more preferably 99.9% by mass or less.

[0088] Specific examples of fillers include inorganic compounds such as silica (more specifically, crystalline silica, fused silica, spherical fused silica, etc.), titanium oxide, zirconium oxide, zinc oxide, tin oxide, silicon nitride, silicon carbide, boron nitride, calcium carbonate, calcium silicate, potassium titanate, aluminum nitride, indium oxide, alumina, antimony oxide, cerium oxide, magnesium oxide, iron oxide, and tin-doped indium oxide (ITO); minerals such as montmorillonite, talc, mica, boehmite, kaolin, smectite, zonolite, vermiculite, and sericite; carbon materials such as carbon black, acetylene black, ketjen black, and carbon nanotubes; metal hydroxides such as aluminum hydroxide and magnesium hydroxide; and various glasses such as glass beads, glass flakes, and glass balloons. These may be used alone or in combination of two or more. Among these, carbon materials are preferred, and carbon nanotubes are more preferred. The use of a carbon material as a conductive filler enables the particles of the present disclosure to be conductive particles.

[0089] The filler is preferably a nanofiller, which means a filler that is a nanomaterial in which at least one dimension (preferably two dimensions, more preferably three dimensions) of the three dimensions indicating the size is about 0.1 nm to 200 nm, and a filler that is a nanostructure constituted by a nanomaterial. Nanofillers tend to be highly agglomerated and difficult to disperse in resins, and the compositions of the present disclosure are particularly effective for such nanofillers.

[0090] The nanofiller is preferably a carbon nanofiller. Specific examples include carbon nanofibers, carbon nanohorns, carbon nanocones, carbon nanotubes, carbon nanostructures, carbon nanocoils, carbon microcoils, carbon nanowalls, carbon nanochaplet, fullerene, carbon black, graphite, graphene, carbon nanoflakes, and derivatives thereof, and one or more of these can be used. Of these, carbon nanotubes (CNTs) are preferred.

[0091] The average diameter of the carbon nanotubes is preferably 0.1 nm or more, more preferably 0.5 nm or more, and even more preferably 1 nm or more, and is preferably 200 nm or less, more preferably 100 nm or less, and even more preferably 50 nm or less. The diameter of carbon nanotubes can be evaluated using a transmission electron microscope. The average diameter is the average of 10 carbon nanotubes.

[0092] The carbon nanotubes are preferably at least one type selected from the group consisting of multi-walled carbon nanotubes and single-walled carbon nanotubes.

[0093] In the particles of the present disclosure, the filler content is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, even more preferably 0.01% by mass or more, and is preferably 30% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, even more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less.

[0094] The compound (I) is not particularly limited as long as it has a plurality of groups (I), and may be a polymer, an oligomer, or a low molecular weight compound other than these.

[0095] The low molecular weight compound (I) is preferably a compound containing a benzene ring or a naphthalene ring. The structure of the polymer or oligomer compound (I) is not particularly limited, and it may or may not contain a benzene ring or a naphthalene ring.

[0096] In group (I), R 1 and R 2 The organic group is as described above.

[0097] R 1 and R 2 Examples of the ring structure formed by bonding include a cyclohexane ring and a benzene ring.

[0098] R 1 and R 2 is preferably hydrogen, and the double line represented by a solid line and a dashed line is preferably a single bond. That is, it is preferable that group (I) is an oxazoline group, and compound (I) is an oxazoline compound.

[0099] Specific examples of oxazoline compounds include low molecular weight oxazoline compounds such as 2-vinyl-2-oxazoline, 4-methyl-2-vinyl-2-oxazoline, 5-methyl-2-vinyl-2-oxazoline, 4-ethyl-2-vinyl-2-oxazoline, 5-ethyl-2-vinyl-2-oxazoline, 4,4-dimethyl-2-vinyl-2-oxazoline, 4,4-diethyl-2-vinyl-2-oxazoline, 4,5-dimethyl-2-vinyl-2-oxazoline, 4,5-diethyl-2-vinyl-2-oxazoline, 2-isopropenyl-2-oxazoline, 4-methyl-2-isopropenyl-2-oxazoline, 5-methyl-2-isopropenyl-2-oxazoline, 4-ethyl-2-isopropenyl-2-oxazoline, 5-ethyl- Examples of the oxazoline compounds include 2-isopropenyl-2-oxazoline, 4,4-dimethyl-2-isopropenyl-2-oxazoline, 4,4-diethyl-2-isopropenyl-2-oxazoline, 4,5-dimethyl-2-isopropenyl-2-oxazoline, 4,5-diethyl-2-isopropenyl-2-oxazoline, 1,3-phenylbisoxazoline [1,3-PBO], and 1,4-phenylbisoxazoline [1,4-PBO]. Examples of the oxazoline compounds in polymer form include homopolymers of the low molecular weight oxazoline compounds described above, such as poly-2-vinyl-2-oxazoline [Pvozo] and poly-2-isopropenyl-2-oxazoline [Pipovo], as well as copolymers of the low molecular weight oxazoline compounds described above with other monomers. These compounds may be used alone or in combination of two or more.

[0100] From the viewpoint of facilitating bonding with the super engineering plastic resin and the filler, the oxazoline compound is preferably an oxazoline group-containing polymer. From the same viewpoint, the oxazoline group-containing polymer preferably contains at least one selected from the group consisting of repeating units derived from 2-vinyl-2-oxazoline and repeating units derived from 2-isopropenyl-2-oxazoline, more preferably at least one selected from the group consisting of Pvozo and Pipovo, and even more preferably Pvozo. The oxazoline group-containing polymer is also preferably a copolymer of 2-vinyl-2-oxazoline or 2-isopropenyl-2-oxazoline with another monomer, more preferably a copolymer of 2-vinyl-2-oxazoline or 2-isopropenyl-2-oxazoline with an acrylic monomer, and even more preferably a copolymer of 2-isopropenyl-2-oxazoline with an acrylic monomer.

[0101] In the oxazoline group-containing polymer, the oxazoline group may be introduced at a terminal, at a side chain, or at both a terminal and a side chain, but it is preferable that the oxazoline group is introduced at least at a terminal.

[0102] The oxazoline group-containing polymer may have a branched structure. When the oxazoline group-containing polymer has a branched structure, the oxazoline group may be contained in the main chain, the branched chain, or both the main chain and the branched chain, but it is preferable that at least the main chain has the oxazoline group, and it is more preferable that the terminal of the main chain has the oxazoline group.

[0103] The molecular weight of the oxazoline group-containing polymer is preferably 2,000 or more, more preferably 5,000 or more, and even more preferably 10,000 or more, and is preferably 400,000 or less, more preferably 300,000 or less, and even more preferably 200,000 or less. The molecular weight of the oxazoline group-containing polymer is a number average molecular weight (Mn), which can be determined based on the PS-converted average molecular weight measured by GPC.

[0104] Specific examples of the compound (I) other than the oxazoline compound include 1,4-bis(benzoxazol-2-yl)naphthalene [1,4-BBN].

[0105] In compound (I), the number of groups (I) may be plural (two or more), but from the viewpoint of facilitating bonding with the super engineering plastic resin and the filler, the number is preferably 10 or more, more preferably 100 or more. The upper limit is not particularly limited, but is usually 1,000 or less.

[0106] In the particles of the present disclosure, the content of compound (I) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, and is preferably 50% by mass or less, more preferably 30% by mass or less, even more preferably 10% by mass or less.

[0107] In the particles of the present disclosure, the coverage of the super engineering plastic resin with Compound (I) is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. The upper limit is not particularly limited and may be 100% by mass, but is usually about 5% by mass. The coverage is determined based on a calibration curve prepared by FT-IR to determine the coverage of the super engineering plastic resin with compound (I). Specifically, the coverage is determined by the following method. Compound (I) was dissolved in propylene glycol monomethyl ether (PGME) at 0.5 mass%, 1.0 mass%, 2.0 mass%, 2.5 mass%, and 3.0 mass% of the super engineering plastic resin to prepare a PGME / compound (I) solution. This solution was mixed with the super engineering plastic resin, then dried to obtain a powder containing the compound (I) mixed with the super engineering plastic resin. This powder was analyzed using FT-IR to measure the absorbance of the group (I) (1670 cm for an oxazoline group). -1 ) and plot it on a graph with absorbance on the y-axis and coating amount (mass%) on the x-axis. A calibration curve is created by drawing an approximation line through these plotted points. The value of x obtained by substituting the absorbance value of group (I) measured by FT-IR using the sample to be measured in the same manner as above into y on the prepared calibration curve is taken as the coverage (mass%) of the super engineering plastic resin with compound (I).

[0108] The particles of the present disclosure may further contain additives, such as crosslinking agents, antistatic agents, heat stabilizers, foaming agents, foam nucleating agents, antioxidants, surfactants, photopolymerization initiators, anti-wear agents, and surface modifiers, which are commonly used in resins.

[0109] The particles of the present disclosure can be produced, for example, by the method for producing particles of the present disclosure described below.

[0110] <Composition> The compositions of the present disclosure include the particles of the present disclosure.

[0111] The composition of the present disclosure may be either a solid or a liquid at 25°C, but is preferably a solid.

[0112] In the composition of the present disclosure, the content of the particles of the present disclosure is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 10% by mass or more. The upper limit is not particularly limited, and may be 100% by mass.

[0113] The composition of the present disclosure may be a dispersion containing the particles of the present disclosure and a solvent. The solvent is not particularly limited and may be water or an organic solvent such as alcohols, ethers, or pyrrolidones. In this case, the content of the particles of the present disclosure in the composition (dispersion) of the present disclosure is preferably 0.1% by mass or more, more preferably 1% by mass or more, even more preferably 10% by mass or more, and is preferably 99% by mass or less, more preferably 80% by mass or less, even more preferably 50% by mass or less.

[0114] The composition of the present disclosure may further contain an additive. As the additive, those described for the particles of the present disclosure can be used.

[0115] <Molded body> The molded article of the present disclosure is obtained by molding the composition of the present disclosure using the composition of the present disclosure. The molding method is not particularly limited, and conventional methods such as injection molding, blow molding, inflation molding, and vacuum / pressure molding can be used.

[0116] The molded article of the present disclosure is suitable for use as a conductive material. In this specification, the term "conductive material" refers to a material having a volume resistivity of 1.0×10 10 Ω·cm or less (preferably 1.0×10 7 Ω·cm or less, preferably 1.0×10 5 Ω·cm or less). For static electricity removal purposes, 10 Ω·cm or less, 10 for applications where conductivity is the goal 5 The lower limit is preferably 1.0×10 Ω·cm or less. 2 The volume resistivity of the molded article of the present disclosure is determined by the following method. The particles are press-molded to obtain a cylindrical compact (radius 6 mm, thickness (height) 100 to 500 μm). The pressing method can be either cold pressing or hot pressing. The resistance of this compact is measured using the four-terminal method, and the volume resistivity (Ω) is calculated using the following formula. Volume resistance (Ω) = voltage (V) / current (I) Then, calculate the volume resistivity (Ω·cm) using the following formula. Volume resistivity (Ω·cm) = Volume resistance value (Ω) × Cross-sectional area of ​​cylinder (cm 2 ) / cylinder thickness (cm) Here, the cross-sectional area of ​​the cylinder is the cross-sectional area of ​​a plane perpendicular to the height direction.

[0117] When the molded article of the present disclosure is used as a conductive material, its application is not particularly limited. For example, it can be used in a wide range of applications, such as static elimination tubes used in pipes, nozzles, shower heads, spray nozzles, rotary nozzles, liquid discharge parts, piping components, liquid transport tubes, liquid transport joints, and lined piping through which fluids pass; fluid transport devices including the static elimination tubes; semiconductor manufacturing devices, pharmaceutical manufacturing devices, pharmaceutical transport devices, chemical manufacturing devices, and chemical transport devices including the fluid transport devices; heater cables; and the like.

[0118] In the molded article of the present disclosure, image analysis of observation with an optical microscope revealed that aggregates with a width of 50 μm or more were 0.3 mm 2 The number of particles per area is preferably 20 or less, more preferably 10 or less, even more preferably 5 or less, and particularly preferably 1 or less. There is no particular lower limit, and the number may be 0. The number of the agglomerates is measured by the following method. The particles are press-molded to obtain a cylindrical compact (radius 6 mm, thickness (height) 100 to 500 μm). The pressing method can be either cold pressing or hot pressing. This compact is observed under an optical microscope, and the obtained image is binarized to calculate the area of ​​the filler portion and analyze the number of aggregates of 50 μm or larger.

[0119] The molded article of the present disclosure can also be suitably used as a dielectric material, particularly as a low-dielectric substrate material (for example, an insulating material). In this specification, the term "low dielectric substrate material" refers to a material having a dielectric constant of 5.0 or less at 25°C and 10 GHz and a dielectric loss tangent of 0.003 or less at 25°C and 10 GHz, more preferably a material having a dielectric constant of 4.0 or less at 25°C and 10 GHz and a dielectric loss tangent of 0.002 or less at 25°C and 10 GHz, and even more preferably a material having a dielectric constant of 3.5 or less at 25°C and 10 GHz and a dielectric loss tangent of 0.0012 or less at 25°C and 10 GHz.

[0120] When the molded article of the present disclosure is used as a dielectric material, its applications are not particularly limited. For example, electrical and electronic components such as connectors, sockets, relay parts, coil bobbins, optical pickups, oscillators, printed wiring boards, and computer-related parts; semiconductor manufacturing process-related parts such as IC trays and wafer carriers; household electrical appliance parts such as VTRs, televisions, irons, air conditioners, stereos, vacuum cleaners, refrigerators, rice cookers, and lighting fixtures; lighting fixture parts such as lamp reflectors and lamp holders; audio product parts such as compact discs and speakers; ferrules for optical cables, telephone parts, facsimile parts, and communication equipment parts such as modems; copier-related parts such as separation claws and heater holders; impellers. It can be used in a wide range of applications, including mechanical parts such as fans, cogwheels, bearings, motor parts and cases, automotive mechanical parts, engine parts, engine room parts, electrical parts, interior parts and other automotive parts, cooking utensils such as microwave cooking pots and heat-resistant tableware, heat insulation and soundproofing materials such as flooring and wall materials, support materials such as beams and pillars, building materials such as roofing materials or civil engineering and construction materials, aircraft, spacecraft, space equipment parts, radiation facility components such as nuclear reactors, marine facility components, cleaning jigs, optical equipment parts, valves, pipes, nozzles, filters, membranes, medical equipment parts and materials, sensor parts, sanitary fixtures, etc.

[0121] The molded article of the present disclosure may be laminated with a metal foil to form a laminate, which is suitable for use as a circuit board, particularly a printed circuit board, a laminated circuit board (multilayer board), or a high-frequency circuit board.

[0122] A high-frequency circuit board is a circuit board that can operate in a high-frequency band. The high-frequency band may be a band of 1 GHz or higher, preferably a band of 3 GHz or higher, and more preferably a band of 5 GHz or higher. There is no particular upper limit, but it may be a band of 100 GHz or lower.

[0123] Examples of metals for the metal foil include aluminum, iron, silver, gold, and ruthenium. Alloys of these metals can also be used. Of these, copper is preferred. Examples of copper that can be used include rolled copper and electrolytic copper.

[0124] The thickness of the laminate is preferably 10 μm to 1000 μm. In the laminate, the molded article of the present disclosure preferably has a thickness of 1 μm to 100 μm. It is preferable that the laminate and the molded body are in the form of a sheet with a substantially uniform thickness, but if there are portions with different thicknesses, the thicknesses are measured at 10 equally spaced points in the longitudinal direction and the average is calculated.

[0125] <Particle manufacturing method> The method for producing particles of the present disclosure includes step 1 of mixing component A with compound (I) having a plurality of groups (I), step 2 of mixing the mixture obtained in step 1 with component B in the presence of a solvent, and step 3 of collecting particles from the dispersion obtained in step 2, wherein component A contains one of a super engineering plastic resin and a filler, and component B contains the other.

[0126] According to the manufacturing method of the present disclosure, one of the super engineering plastic resin and the filler is bonded to the compound (I) in step 1, and the other of the super engineering plastic resin and the filler is bonded to the compound (I) in step 2. Then, by collecting the particles from the dispersion in step 3, it is possible to efficiently manufacture particles in which the super engineering plastic resin and the filler are bonded via the compound (I).

[0127] (Process 1) In step 1, component A is mixed with compound (I) having a plurality of groups (I). As a result, functional groups present on the surface of component A, such as carboxy groups, phenolic OH groups, and thiol groups, bond with the groups (I) of compound (I), thereby bonding component A and compound (I).

[0128] Component A may be either a super engineering plastic resin or a filler, but is preferably a super engineering plastic resin.

[0129] Both a super engineering plastic resin and a filler may be added as component A. In this case, it is preferable that either one of them accounts for 95% by mass or more of component A, and it is more preferable that the super engineering plastic resin accounts for 95% by mass or more.

[0130] The super engineering plastic resin, filler, and compound (I) are the same as those described for the particles of the present disclosure.

[0131] The amount of compound (I) added is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 0.1% by mass or more, relative to the amount of component A added, and is preferably 50% by mass or less, more preferably 30% by mass or less, even more preferably 10% by mass or less.

[0132] Although a solvent is not essential for the mixing in step 1, mixing may be performed in the presence of a solvent. The solvent is not particularly limited and may be water or an organic solvent such as an alcohol, an ether, or a pyrrolidone, but an organic solvent is preferred, and an ether is more preferred.

[0133] The amount of solvent added is preferably 1 time or more, more preferably 5 times or more, and even more preferably 10 times or more, the total mass of Component A and Compound (I), and is preferably 500 times or less, more preferably 200 times or less, and even more preferably 100 times or less.

[0134] The mixing method in step 1 is not particularly limited and may be appropriately selected depending on the types and amounts of materials, etc. For example, when mixing is performed in the presence of a solvent, mixing can be performed using ultrasound or a homogenizer. The mixing time is preferably 5 minutes to 48 hours, and the mixing temperature is preferably room temperature to 200°C.

[0135] The mixing in step 1 may be carried out once or multiple times. The materials may be added all at once or in portions. The same applies to step 2 described below.

[0136] When the mixing in step 1 is carried out in the presence of a solvent, the dispersion obtained after mixing may be used as is in step 2, or the solvent may be removed from the dispersion by centrifugation or the like before use in step 2.

[0137] (Process 2) In step 2, the mixture obtained in step 1 (containing component A conjugated with compound (I)) is mixed with component B in the presence of a solvent. As a result, functional groups present on the surface of component B, such as carboxyl groups, phenolic OH groups, and thiol groups, bond with group (I) of compound (I) in the mixture obtained in step 1, and components A and B are conjugated via compound (I).

[0138] Step 2 may be a step of mixing component A conjugated with compound (I) and component B in the presence of a solvent.

[0139] Component B may be either a super engineering plastic resin or a filler, but is preferably a filler.

[0140] Both the super engineering plastic resin and the filler may be added as component B. In this case, the component that was 5% by mass or less in component A used in step 1 preferably accounts for 95% by mass or more in component B, and it is more preferable that the filler in component B accounts for 95% by mass or more.

[0141] The amount of component B added is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and even more preferably 0.1% by mass or more, relative to the amount of component A added in step 1, and is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less.

[0142] The solvent used in step 2 is not particularly limited, as in step 1, and may be water or an organic solvent such as alcohols, ethers, or pyrrolidones, but organic solvents are preferred, and pyrrolidones are more preferred. The solvent may be used alone or in combination of two or more.

[0143] The solvent may also contain a dispersion stabilizer. The necessity and type of dispersion stabilizer can be determined depending on the filler used. For example, when carbon nanotubes with a large diameter are used, a dispersion stabilizer is not necessary.

[0144] The amount of solvent added is preferably 1 time or more, more preferably 5 times or more, and even more preferably 10 times or more of the total mass of the mixture obtained in step 1 (or the solid content thereof if it is a dispersion) and component B, and is preferably 500 times or less, more preferably 200 times or less, and even more preferably 100 times or less.

[0145] As with step 1, the mixing method in step 2 is not particularly limited and may be selected appropriately depending on the types and amounts of materials. The mixing time is preferably 5 minutes to 48 hours, and the mixing temperature is preferably room temperature to 200°C.

[0146] (Step 3) In step 3, particles are collected from the dispersion obtained in step 2. The method for collecting particles is not particularly limited, but examples thereof include centrifugation.

[0147] The conditions for centrifugation are not particularly limited as long as the precipitate and the solvent are separated, but for example, centrifugation may be performed at 1,000 to 50,000 rpm for 1 to 60 minutes. After centrifugation, the precipitate is dried to collect the particles. Before drying, the precipitate may be washed with methanol or the like.

[0148] The preferred forms described above for the particles of the present disclosure are also applicable to particles obtained by the production method of the present disclosure.

[0149] Although the embodiments have been described above, it will be understood that various changes in form and details can be made without departing from the spirit and scope of the claims. [Example]

[0150] The present disclosure will now be described in more detail with reference to examples, but the present disclosure is not limited to these examples.

[0151] The materials used in the examples are as follows: (Super engineering plastic resin) FEP (TFE unit / HFP unit (molar ratio) = 88.0 / 12.0, melting point: 260°C, thermal decomposition temperature: 430°C, continuous use temperature: 200°C) PFA (TFE unit / PPVE unit (molar ratio) = 97.9 / 2.1, melting point: 300°C, thermal decomposition temperature: 430°C, continuous use temperature: 200°C) PES (Mitsui Fine Chemicals, glass transition temperature: 225°C, thermal decomposition temperature: 465°C, continuous use temperature: 190°C) LCP (copolymer of parahydroxybenzoic acid, biphenol, and terephthalic acid, melting point: 343°C, thermal decomposition temperature: 520°C, continuous use temperature: 240°C) PEEK (Solvay, melting point: 339°C, thermal decomposition temperature: 553°C, continuous use temperature: 240°C) (filler) MWCNT (multi-walled carbon nanotubes, average diameter: 9 nm) SWCNT (single-walled carbon nanotube, average diameter: 2 nm) (Compound (I) (Oxazoline Compound)) Pvozo (Poly-2-vinyl-2-oxazoline, molecular weight: 48,000) WS300 (Nippon Shokubai Co., Ltd. "Epocross WS300", copolymer of 2-isopropenyl-2-oxazoline and acrylic ester, molecular weight: 40,000) (solvent) PGME (Propylene Glycol Monomethyl Ether) PVP (Polyvinylpyrrolidone) NMP (N-methyl-2-pyrrolidone) water

[0152] Example 1 <Sample Preparation> (Process 1) 3 g of FEP aggregates and 30 g of PGME were placed in a 50 cc sample vial. The aggregates were broken down into small pieces with a spatula and subjected to ultrasonication for 15 minutes using an ultrasonic homogenizer. Pvozo was added to the concentrated Pvozo / PGME solution at a concentration of 4% by mass relative to the FEP. The mixture was subjected to ultrasonication for 10 minutes at room temperature using a bath-type ultrasonicator. A stirrer was added and the mixture was reacted in an oil bath at 100°C for 24 hours. After 24 hours, the sample was removed from the oil bath. The mixture was centrifuged at 4000 rpm for 5 minutes. The supernatant PGME was removed, and 10 g of methanol was added. The mixture was stirred with a spatula and washed with methanol. The mixture was centrifuged at 4000 rpm for 5 minutes, and the methanol was removed. This methanol washing procedure (adding methanol, centrifuging, and removing methanol) was repeated five times. The mixture was then dried in a vacuum dryer at 40°C for 3 hours under a vacuum pressure of 1.33 kPa to obtain FEP / Pvozo powder.

[0153] (Process 2) 1.2 g of FEP / Pvozo powder and 10 g of NMP were placed in a 50 cc sample vial. Ultrasonication was performed for 15 minutes using a bath-type ultrasonicator. MWCNT was added from the MWCNT dispersion so that the concentration was 0.1 mass% relative to the FEP / Pvozo powder. Ultrasonication was performed for 10 minutes at room temperature using a bath-type ultrasonicator. A stirrer was added, and the mixture was allowed to react for 2 hours at 100°C in an oil bath, yielding a FEP / Pvozo / MWCNT composite. After 2 hours, the sample was removed from the oil bath.

[0154] (Step 3) The mixture was centrifuged at 4000 rpm for 5 minutes to separate the FEP / PVC / MWCNT composite from the uncoated MWCNT. The NMP solvent in which the MWCNT was dispersed was removed with a pipette. The supernatant NMP was removed, 10 g of methanol was added, and the mixture was stirred with a spatula and washed with methanol. This methanol washing procedure (adding methanol, centrifuging, and removing the methanol) was repeated five times. The mixture was then dried in a vacuum dryer at 40°C for 3 hours under a vacuum pressure of 1.33 kPa to obtain particles in which FEP and MWCNT were bonded via an oxazoline compound.

[0155] The particles obtained above and the powder obtained after step 1 were measured and evaluated using the following methods.

[0156] <Coverage> Oxazoline compound (PGME) was dissolved in PGME at 0.5 mass%, 1.0 mass%, 2.0 mass%, 2.5 mass%, and 3.0 mass% of super engineering plastic resin (FEP) to prepare a PGME / oxazoline compound solution. This solution was mixed with super engineering plastic resin, then dried to obtain a powder containing the oxazoline compound mixed with the super engineering plastic resin. This powder was analyzed using FT-IR to measure the 1670 cm of the oxazoline group. -1 The absorbance was read and plotted on a graph with absorbance on the y-axis and coating amount (mass%) on the x-axis. A calibration curve was created by drawing an approximation line through these plotted points. Using the powder after step 1 (FEP / Pvozo powder) to be measured, the absorbance value of the oxazoline group measured by FT-IR in the same manner as above was substituted for y in the calibration curve created, and the value of x obtained was used as the coverage rate (mass%) of the super engineering plastic resin by the oxazoline compound.

[0157] <Volume resistivity> The particles obtained in Examples 1 to 3 and Comparative Example 1 were placed in a disk with a radius of 6 mm and cold-press molded using a hand press at room temperature to obtain a cylindrical molded body (radius 6 mm, thickness (height) 100 to 500 μm). The resistance of this molded body was measured by the four-terminal method, and the volume resistivity (Ω) was calculated using the following formula. The particles obtained in Example 4 were hot-press molded to obtain a molded body. The molding conditions were preheating at 280°C for 10 minutes, pressure pressing at 3 MPa for 1 minute, and cooling at 3 MPa for 5 minutes. The resistance of this molded body was measured by the four-terminal method as described above, and the volume resistance (Ω) was calculated using the following formula: The particles obtained in Example 5 were hot-press molded to obtain a molded body. The molding conditions were preheating at 330°C for 15 minutes, pressure pressing at 3 MPa for 1 minute, and cooling at 3 MPa for 5 minutes. The resistance of this molded body was measured by the four-terminal method as described above, and the volume resistance (Ω) was calculated using the following formula. The particles obtained in Example 6 were hot-press molded to obtain a molded body. The molding conditions were preheating at 390°C for 10 minutes, pressure pressing at 3 MPa for 1 minute, and cooling at 3 MPa for 5 minutes. The resistance of this molded body was measured by the four-terminal method as described above, and the volume resistance (Ω) was calculated using the following formula: Volume resistance (Ω) = voltage (V) / current (I) Then, the volume resistivity (Ω·cm) was calculated using the following formula. Volume resistivity (Ω·cm) = Volume resistance value (Ω) × Cross-sectional area of ​​cylinder (cm 2 ) / cylinder thickness (cm) Here, the cross-sectional area of ​​the cylinder is the cross-sectional area of ​​a plane perpendicular to the height direction.

[0158] <Dispersed state> The molded body used in the measurement of volume resistivity was observed under an optical microscope, and the obtained image was subjected to binarization processing to calculate the area of ​​the filler (CNT) portion and analyze the number of agglomerates of 50 μm or more. 2 Those with 20 or fewer particles per area were marked with a circle, and those with more than 20 particles were marked with an X. The results are shown in Table 1. An optical microscope photograph of the molded product is shown in FIG. In the optical microscope photograph of Example 1 (FIG. 1), a network of CNTs can be seen, but this is not because the CNTs are aggregated, but because the CNTs are finely dispersed in the FEP (super engineering plastic resin).

[0159] Example 2 and Comparative Example 1 Particles were prepared in the same manner as in Example 1 except that the type and amount of each component was changed as shown in Table 1, and measurements and evaluations were carried out in the same manner as in Example 1. The results are shown in Table 1. Optical microscope photographs of the molded bodies of Example 2 and Comparative Example 1 are shown in Figures 2 and 3, respectively.

[0160] Example 3 The super engineering plastic resin was changed from FEP to PFA, and the solvent used in step 1 was changed from PGME to water. Furthermore, the NMP used in step 2 was changed to water. Particles were produced in the same manner as in Example 1, except that the type and amount of each component was changed as shown in Table 1, and measurements and evaluations were carried out in the same manner as in Example 1. The results are shown in Table 1. An optical microscope photograph of the molded product of Example 3 is shown in FIG. 4.

[0161] Example 4 The super engineering plastic resin was changed from FEP to PES (polyethersulfone), and the solvent used in step 1 was changed from PGME to water. Furthermore, the NMP used in step 2 was changed to water. Particles were produced in the same manner as in Example 1, except that the type and amount of each component was changed as shown in Table 1, and measurements and evaluations were carried out in the same manner as in Example 1. The results are shown in Table 1. An optical microscope photograph of the molded product of Example 4 is shown in FIG. 5.

[0162] Example 5 The super engineering plastic resin was changed from FEP to LCP (liquid crystal polymer), and the solvent used in step 1 was changed from PGME to water. Furthermore, the NMP used in step 2 was changed to water. Particles were produced in the same manner as in Example 1, except that the type and amount of each component was changed as shown in Table 1, and measurements and evaluations were carried out in the same manner as in Example 1. The results are shown in Table 1. An optical microscope photograph of the molded product of Example 5 is shown in FIG. 6.

[0163] Example 6 The super engineering plastic resin was changed from FEP to PEEK (polyether ether ketone), and the solvent used in step 1 was changed from PGME to water. Furthermore, the NMP used in step 2 was changed to water. Particles were produced in the same manner as in Example 1, except that the type and amount of each component was changed as shown in Table 1, and measurements and evaluations were carried out in the same manner as in Example 1. The results are shown in Table 1.

[0164] [Table 1]

Claims

1. The composition includes a super engineering plastic resin, a filler, and a compound (I) having a plurality of groups (I) represented by the following formula: Particles in which the super engineering plastic resin and the filler are bonded via the compound (I). 【Chemical 1】 (In the formula, R １ and R ２ are the same or different and represent hydrogen or an organic group, and may be bonded to each other to form a ring structure. A double line represented by a solid line and a dashed line represents a single bond or a double bond.

2. 2. The particles according to claim 1, wherein the super engineering plastic resin has a thermal decomposition temperature of 330° C. or higher.

3. 3. The particles according to claim 1, wherein the super engineering plastic resin has a continuous use temperature of 140° C. or higher.

4. 3. The particle according to claim 1, wherein the super engineering plastic resin is at least one selected from the group consisting of fluororesin, liquid crystal polymer, polyetherimide, polyphenylene sulfide, polyaryletherketone, polysulfone, and polyethersulfone.

5. 3. The particles according to claim 1, wherein the super engineering plastic resin is at least one selected from the group consisting of fluororesin, liquid crystal polymer, polyaryletherketone, and polyethersulfone.

6. 3. The particles according to claim 1, wherein the super engineering plastic resin is a perfluororesin.

7. 3. The particle according to claim 1, wherein the super engineering plastic resin is at least one selected from the group consisting of polytetrafluoroethylene, tetrafluoroethylene / perfluoro(alkyl vinyl ether) copolymer, and tetrafluoroethylene / hexafluoropropylene copolymer.

8. 3. The particles according to claim 1, wherein the super engineering plastic resin is at least one selected from the group consisting of tetrafluoroethylene / perfluoro(alkyl vinyl ether) copolymer and tetrafluoroethylene / hexafluoropropylene copolymer.

9. 3. The particle according to claim 1, wherein the filler is a nanofiller.

10. 3. The particle according to claim 1, wherein the filler is a carbon nanotube.

11. 3. The particle according to claim 1, wherein the filler is at least one selected from the group consisting of multi-walled carbon nanotubes and single-walled carbon nanotubes.

12. 3. The particles according to claim 1, wherein the content of the filler is 0.001 to 30% by mass.

13. 3. The particle according to claim 1, wherein the group (I) is an oxazoline group and the compound (I) is an oxazoline compound.

14. The particle according to claim 13, wherein the oxazoline compound is an oxazoline group-containing polymer.

15. 15. The particle according to claim 14, wherein the molecular weight of the oxazoline group-containing polymer is 2,000 to 400,000.

16. 15. The particle according to claim 14, wherein the oxazoline group-containing polymer comprises at least one repeating unit selected from the group consisting of a repeating unit derived from 2-vinyl-2-oxazoline and a repeating unit derived from 2-isopropenyl-2-oxazoline.

17. 15. The particles according to claim 14, wherein the oxazoline group-containing polymer is poly-2-vinyl-2-oxazoline.

18. 15. The particles according to claim 14, wherein the oxazoline group-containing polymer is a copolymer of 2-isopropenyl-2-oxazoline and an acrylic monomer.

19. 3. The particles according to claim 1, wherein the content of the compound (I) is 0.01 to 50% by mass.

20. The particles according to claim 1 or 2, wherein the content of the super engineering plastic resin is 80 to 99.9% by mass, the content of the filler is 0.01 to 0.5% by mass, and the content of the compound (I) is 0.1 to 10% by mass.

21. A composition comprising the particles of claim 1 or 2.

22. 22. The composition of claim 21, which is a solid or liquid at 25°C.

23. A molded article made using the composition according to claim 21.

24. Volume resistivity is 1.0 x 10 １０ The molded article according to claim 23, having a resistivity of Ω·cm or less.

25. In image analysis using an optical microscope, aggregates with a width of 50 μm or more were found to be 0.3 mm ２ 24. The molded article according to claim 23, wherein the number of particles per unit area is 20 or less.

26. Step 1: mixing component A with compound (I) having a plurality of groups (I) represented by the following formula: Step 2: mixing the mixture obtained in step 1 with component B in the presence of a solvent; and Step 3 includes collecting particles from the dispersion obtained in step 2, A method for producing particles, wherein the component A contains one of a super engineering plastic resin and a filler, and the component B contains the other. 【Chemistry 2】 (In the formula, R １ and R ２ are the same or different and represent hydrogen or an organic group, and may be bonded to each other to form a ring structure. A double line represented by a solid line and a dashed line represents a single bond or a double bond.

27. The method for producing particles according to claim 26, wherein in step 1, component A and compound (I) are mixed in the presence of a solvent.

28. 27. The method for producing particles according to claim 26, wherein in step 2, component A conjugated with compound (I) and component B are mixed in the presence of a solvent.

29. 27. The method for producing particles according to claim 26, wherein in step 3, the particles are collected from the dispersion obtained in step 2 by centrifugation.

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