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

Abstract

The purpose of the present disclosure is to provide: particles in each of which a filler is sufficiently dispersed in a resin; a composition; a molded body; and a method for producing particles. The present disclosure provides particles which each contain a super engineering plastic resin, a filler, and a compound (I) that has a plurality of groups (I) represented by the 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.)

Description

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

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

[0002] Various studies have been 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 having excellent electrical properties can be obtained by blending a fluororesin with carbon nanotubes that have been surface-treated with a fluorine-based surfactant.

[0003] Japanese Patent Application Laid-Open No. 2005-146081

[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.

[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). (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.

[0007] The present disclosure (2) is the particle according to the present disclosure (1), wherein the thermal decomposition temperature of the super engineering plastic resin is 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 the 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 the 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 a fluororesin, a liquid crystal polymer, a polyaryl ether ketone, and a 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 the 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 the 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), wherein the content of the filler is 0.001 to 30 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), wherein 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), wherein 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), wherein 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 comprising 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] The present disclosure (24) has a volume resistivity of 1.0 × 10 １０ The molded body according to the present disclosure (23) has a hardness 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 are 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: (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), wherein 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, particles are collected from the dispersion liquid obtained in the step 2 by centrifugation.

[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.

[0036] A micrograph showing the dispersion state of Example 1. A micrograph showing the dispersion state of Example 2. A micrograph showing the dispersion state of Comparative Example 1. A micrograph showing the dispersion state of Example 3. A micrograph showing the dispersion state of Example 4. A micrograph showing the dispersion state of Example 5.

[0037] In this specification, the term "organic group" refers to 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" include an alkyl group which may have one or more substituents, an alkenyl group which may have one or more substituents, an alkynyl group which may have one or more substituents, a cycloalkyl group which may have one or more substituents, a cycloalkenyl group which may have one or more substituents, a cycloalkadienyl group which may have one or more substituents, an aryl group which may have one or more substituents, an aralkyl group which may have one or more substituents, a non-aromatic heterocyclic group which may have one or more substituents, a heteroaryl group which may have one or more substituents, a cyano group, a formyl group, RaO-, RaCO-, and RaSO. ２ -, RaCOO-, RaNRaCO-, RaCONRa-, RaOCO-, RaOSO ２ - and RaNRbSO ２- (In these formulas, Ra is independently an alkyl group which may have one or more substituents, an alkenyl group which may have one or more substituents, an alkynyl group which may have one or more substituents, a cycloalkyl group which may have one or more substituents, a cycloalkenyl group which may have one or more substituents, a cycloalkadienyl group which may have one or more substituents, an aryl group which may have one or more substituents, an aralkyl group which may have one or more substituents, a non-aromatic heterocyclic group which may have one or more substituents, or a heteroaryl group which may have one or more substituents; and Rb is independently H or an alkyl group which may have one or more substituents). As the organic group, an alkyl group which may have one or more substituents is preferred.

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

[0039] <Particle> The particle of the present disclosure includes 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). (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.

[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 preferably 560°C or lower, more preferably 540°C or lower, even more preferably 520°C or lower. The thermal decomposition temperature of the super engineering plastic resin is measured using a thermal analyzer STA7200 manufactured by Hitachi High-Tech Science Corporation. The measurement was performed in 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 heating rate of 10°C / min. The temperature at which the mass decreases 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 properties of the resin deteriorate by 50% from their initial values ​​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], still more preferably at least one selected from the group consisting of PFA and FEP, and particularly preferably FEP.

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

[0047] Modified monomer is not particularly limited as long as it can be copolymerized with TFE, and for example, can be listed perfluoroolefin such as hexafluoropropylene [HFP]; chlorofluoroolefin such as chlorotrifluoroethylene [CTFE]; hydrogen-containing fluoroolefin such as trifluoroethylene, vinylidene fluoride [VdF]; perfluorovinyl ether; perfluoroalkyl allyl ether; (perfluoroalkyl) ethylene; ethylene etc. Also, the modified monomer used can be one kind or multiple kinds.

[0048] The perfluorovinyl ether is not particularly limited, and examples thereof include perfluorovinyl ethers represented by the following general formula (1): ２ ═CF—ORf (1) (wherein Rf represents a perfluoroorganic group). In this specification, the term "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], where Rf in general formula (1) 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 a perfluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, a perfluorobutyl group, a perfluoropentyl group, and a perfluorohexyl group. Preferred is perfluoro(propyl vinyl ether) [PPVE], in which the perfluoroalkyl group is a perfluoropropyl group.

[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]

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

[0054]

[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 modified monomer unit is preferably in the range of 0.00001 to 1.0 mass%. The lower limit of the content of the modified monomer unit is more preferably 0.0001 mass%, even more preferably 0.001 mass%, even more preferably 0.005 mass%, particularly preferably 0.010 mass%, and particularly preferably 0.030 mass%. The upper limit of the content of the modified monomer unit is preferably 0.90 mass%, more preferably 0.50 mass%, even more preferably 0.40 mass%, and even more preferably 0.30 mass%. In this specification, the modified monomer unit refers to 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] The PFA is not particularly limited, but is preferably a copolymer in which the molar ratio of TFE units to PAVE units (TFE units / PAVE units) is 70 / 30 or more and less than 99 / 1. 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 monomers copolymerizable with TFE and PAVE (a copolymer in which the total content of TFE units and PAVE units is 90 to 99.9 mol %), 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 (CF ２ ) ｎ Z ４ (In the formula, Z １ , Z ２ and 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): CF ２ =CF-OCH ２ -Rf １ (wherein, 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, Rf ４represents a perfluoroalkyl group having 1 to 5 carbon atoms.) Examples of the allyl ether monomer include an allyl ether monomer represented by CH ２ =CFCF ２ -O-Rf ４ , C.F. ２ =CFCF ２ -O-Rf ４ (perfluoroalkyl allyl ether), CF ２ =CFCH ２ -O-Rf ４ , C.H. ２ = CHCF ２ -O-Rf ４ (wherein, Rf ４ is the same as the above formula (X). Further examples of the monomer 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 180 to less than 324° C., more preferably 230 to 320° C., and even more preferably 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] FEP is not particularly limited, but the copolymer in which the molar ratio of TFE unit and HFP unit (TFE unit / HFP unit) is 70 / 30 or more and less than 99 / 1 is preferred.More preferably, the molar ratio is 70 / 30 or more and 98.9 / 1.1 or less, and even more preferably, the molar ratio is 80 / 20 or more and 98.9 / 1.1 or less.The FEP preferably contains 0.1 to 10 mol% of the monomer unit derived from the monomer copolymerizable with TFE and HFP (the copolymer in which the total of TFE unit and HFP unit is 90 to 99.9 mol%), 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 150 to less than 324° C., more preferably 200 to 320° C., and even more preferably 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. 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 includes a monomer represented by the following formula CH ２ =CX １ Rf ２ , C.F. ２ = CFRf ２ , C.F. ２ =CFORf ２ , C.H. ２ = C(Rf ２ ) ２ (In the formula, X １ is a hydrogen atom or a fluorine atom, Rf ２represents a fluoroalkyl group which may contain an ether bond.) and a monomer represented by formula (X), among which CF ２ = CFRf ２ , C.F. ２ =CFORf ２ and CH ２ =CX １ Rf ２ and a monomer represented by formula (X), and HFP, CF ２ =CF-ORf ３ (wherein, Rf ３ represents a perfluoroalkyl group having 1 to 5 carbon atoms; ２ =CF-CF ２ -O-Rf ４ (wherein, Rf ４ represents a perfluoroalkyl group having 1 to 5 carbon atoms; ２ is a fluoroalkyl group having 1 to 8 carbon atoms, ２ =CX １ Rf ２ Further, examples of the monomer copolymerizable with TFE and ethylene 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 140 to less than 324° C., more preferably 160 to 320° C., and even more preferably 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 carbon number of 10 ６Each of the polymers 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, a fluororesin is melt-extruded to produce a film having 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 as follows: N = I x K / t (A), where I is absorbance, K is correction coefficient, and t is 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, such as, for example, Type I liquid crystal polymer (such as biphenol / benzoic acid / parahydroxybenzoic acid (POB) copolymer), Type II liquid crystal polymer (such as hydroxynaphthoic acid (HNA) / POB copolymer), and Type III liquid crystal polymer (such as POB / ethylene terephthalate copolymer). 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, and p,p'-biphenylene ether. Of 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] There are no particular restrictions on the polysulfone, and any common 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 obtained when a differential scanning calorimeter (DSC) is used to raise the temperature at a rate of 10°C / min. The glass transition temperatures of polyetherimides, polysulfones, and polyethersulfones can be obtained by raising the temperature of 10 mg of a sample at 10°C / min using a differential scanning calorimeter (DSC822e, manufactured by Mettler Toledo), and then measuring the temperature at the midpoint between the two intersections of an extension of the baseline before and after the second-order transition of the DSC curve and a 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. By using a carbon material as a conductive filler, the particles of the present disclosure can be made into conductive particles.

[0089] The filler is preferably a nanofiller. Nanofiller refers to a filler that is a nanomaterial, at least one of the three dimensions (preferably two dimensions, more preferably three dimensions) of which is approximately 0.1 nm to 200 nm, and a filler that is a nanostructure composed of nanomaterials. Nanofillers tend to have a high tendency to aggregate and are difficult to disperse in resins. The composition of the present disclosure is 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 nanochaplets, fullerenes, carbon black, graphite, graphene, carbon nanoflakes, and derivatives thereof. One or more of these may 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 the 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 ２is 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 the oxazoline compound 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 compound 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 compound polymer 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 may be used alone or in combination of two or more.

[0100] From the viewpoint of ease of forming a bond 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, even more preferably 10,000 or more, and is preferably 400,000 or less, more preferably 300,000 or less, even more preferably 200,000 or less. The molecular weight of the oxazoline group-containing polymer is a number average molecular weight (Mn), and 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 of groups (I) 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 typically about 5% by mass. The coverage is determined based on a calibration curve prepared using 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) is dissolved in propylene glycol monomethyl ether (PGME) to give 0.5%, 1.0%, 2.0%, 2.5%, and 3.0% by mass of the super engineering plastic resin, respectively, to prepare a PGME / compound (I) solution. This solution is mixed with the super engineering plastic resin and then dried to obtain a powder in which compound (I) is mixed with the super engineering plastic resin. This powder is analyzed using FT-IR to measure the absorbance of group (I) (1670 cm for an oxazoline group). －１ ) is read and plotted on a graph with absorbance on the y-axis and coverage (mass%) on the x-axis. A calibration curve is prepared by drawing an approximation line through these plotted points. The absorbance value of group (I), measured by FT-IR using the sample to be measured in the same manner as above, is substituted for y in the prepared calibration curve, and the value of x obtained is taken as the coverage (mass%) of the super engineering plastic resin by 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 composition of the present disclosure comprises 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, and even more preferably 10% by mass or more, and is preferably 99% by mass or less, more preferably 80% by mass or less, and 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 Article> The molded article of the present disclosure is obtained by molding the composition of the present disclosure. The molding method is not particularly limited, and a conventional method such as injection molding, blow molding, inflation molding, or vacuum / pressure molding can be used.

[0116] The molded article of the present disclosure is suitably used 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, more preferably 1.0 × 10 ５ Ω cm or less). １０ Ω cm or less, and 10 for applications where conductivity is the goal ５ The lower limit is not particularly limited, but is preferably 1.0 × 10 ２ A value of about Ω·cm is preferred. The volume resistivity of the molded body of the present disclosure is determined by the following method. The particles are press-molded to obtain a cylindrical molded body (radius 6 mm, thickness (height) 100 to 500 μm). The pressing method may be either cold pressing or hot pressing. The resistance of this molded body is measured using the four-terminal method, and the volume resistance value (Ω) is calculated using the following formula: Volume resistance value (Ω) = Voltage (V) / Current (I) Then, the volume resistivity (Ω·cm) is calculated using the following formula: Volume resistivity (Ω·cm) = Volume resistance value (Ω) × Cross-sectional area of ​​cylinder (cm ２ ) / thickness of cylinder (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, lined piping, etc. 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; etc.

[0118] In the molded article of the present disclosure, image analysis of observation with an optical microscope revealed that the number of aggregates with a width of 50 μm or more was 0.3 mm ２The number of agglomerates 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 it may be 0. The number of agglomerates is measured by the following method. The particles are press-molded to obtain a cylindrical molded body (radius 6 mm, thickness (height) 100 to 500 μm). The pressing method may be either cold pressing or hot pressing. This molded body is observed under an optical microscope, and the obtained image is subjected to a binarization process to calculate the area of ​​the filler portion and analyze the number of agglomerates of 50 μm or more.

[0119] The molded article of the present disclosure can also be suitably used as a dielectric material, particularly a low-dielectric substrate material (e.g., 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 application is 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. Such a laminate 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] The 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 the band may be 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. Furthermore, in the laminate, the thickness of the molded article of the present disclosure is preferably 1 μm to 100 μm. It is preferable that the laminate and molded article 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 of these thicknesses is used.

[0125] <Method for Producing Particles> The method for producing particles according to 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] (Step 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 the super engineering plastic resin and the 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 the 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 selected appropriately depending on the type and amount of materials. For example, when mixing in the presence of a solvent, ultrasonic waves or a homogenizer can be used. 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, and then the dispersion may be used in step 2.

[0137] (Step 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 such as carboxy groups, phenolic OH groups, and thiol groups present on the surface of component B bond with group (I) of compound (I) in the mixture obtained in step 1, and component A and component 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 its solid content 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] The mixing method in step 2 is not particularly limited, as in step 1, and may be appropriately selected depending on the types and amounts of materials, etc. 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 carried out 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.

[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 (manufactured by 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 (manufactured by 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 nanotubes, average diameter: 2 nm) (Compound (I) (oxazoline compound)) Pvozo (poly-2-vinyl-2-oxazoline, molecular weight: 48,000) WS300 ("Epocross WS300" manufactured by Nippon Shokubai Co., Ltd., a 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> (Step 1) 3 g of FEP aggregates and 30 g of PGME were added to a 50 cc sample vial. The aggregates were broken down into small pieces with a spatula, and ultrasonic waves were applied for 15 minutes using an ultrasonic homogenizer. Pvozo was added to a concentrated Pvozo / PGME solution so that the concentration was 4% by mass relative to the FEP. Ultrasonic waves were applied for 10 minutes at room temperature using a bath-type ultrasonic wave. A stirrer was added, and the mixture was allowed to react for 24 hours at 100°C using an oil bath. After 24 hours, the sample was removed from the oil bath. Separation was performed using a centrifuge 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. Separation was performed using a centrifuge 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 dried using a vacuum dryer under a vacuum pressure of 1.33 kPa at 40° C. for 3 hours to obtain a powder of FEP / Pvozo.

[0153] (Step 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 to the FEP / Pvozo powder at a concentration of 0.1% by mass. 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 to obtain 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 using a centrifuge to separate the FEP / Pvozo / MWCNT composite from the uncoated MWCNT. The NMP solvent in which the MWCNT was dispersed was removed using a pipette. The supernatant NMP was removed, 10 g of methanol was added, the mixture was stirred with a spatula, and the mixture was washed with methanol. This methanol washing procedure (adding methanol, centrifuging, and removing methanol) was repeated five times. The mixture was dried using 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 by the following methods.

[0156] <Coverage> An oxazoline compound (Pvozo) was dissolved in PGME to give a coverage of 0.5 mass%, 1.0 mass%, 2.0 mass%, 2.5 mass%, and 3.0 mass% relative to the super engineering plastic resin (FEP), respectively, to prepare a PGME / oxazoline compound solution. This solution was mixed with the super engineering plastic resin, and then dried to obtain a powder in which the oxazoline compound was 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 coverage (mass%) on the x-axis. A calibration curve was created by drawing an approximation line through these plotted points. The powder (FEP / Pvozo powder) after step 1 was used to measure, and the absorbance value of the oxazoline group was measured by FT-IR in the same manner as above. The value of x obtained by substituting the y value for the y value of the calibration curve was used to determine the coverage (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 a 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: 280°C, 10 min, pressure pressing: 3 MPa, 1 min, and cooling: 3 MPa, 5 min. The resistance of this molded body was measured by the four-terminal method in the same manner as above, and the volume resistivity (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: 330°C, 15 min, pressure pressing: 3 MPa, 1 min, and cooling: 3 MPa, 5 min. The resistance of this molded body was measured by the four-terminal method in the same manner as above, and the volume resistance value (Ω) was calculated by the following formula. The particles obtained in Example 6 were hot-press molded to obtain a molded body. The molding conditions were preheating: 390°C, 10 min, pressure pressing: 3 MPa, 1 min, cooling: 3 MPa, 5 min. The resistance of this molded body was measured by the four-terminal method in the same manner as above, and the volume resistance value (Ω) was calculated by the following formula. Volume resistance value (Ω) = voltage (V) / current (I) Then, the volume resistivity (Ω cm) was calculated by the following formula. Volume resistivity (Ω cm) = volume resistance value (Ω) × cross-sectional area of ​​cylinder (cm ２ ) / thickness of cylinder (cm) Here, the cross-sectional area of ​​the cylinder is the cross-sectional area of ​​a plane perpendicular to the height direction.

[0158] <Dispersion state> The molded body used in the measurement of volume resistivity was observed under an optical microscope, the obtained image was subjected to binarization processing, the area of ​​the filler (CNT) portion was calculated, and the number of agglomerates of 50 μm or more was analyzed. ２ Those with 20 or less CNTs per area were rated as ◯, and those with more than 20 CNTs were rated as ×. The results are shown in Table 1. An optical microscope photograph of the molded product is shown in Figure 1. Note that, although a mesh-like CNT can be seen in the optical microscope photograph of Example 1 (Figure 1), this is not due to aggregation of CNTs, but rather due to the CNTs being finely dispersed in 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 types and amounts of each component were 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. In addition, 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 Figure 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. In addition, 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 Figure 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. In addition, 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 Figure 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. In addition, the NMP used in step 2 was changed to water. Particles were produced in the same manner as in Example 1, except that the types and amounts of each component were 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]

Claims

1. Particles 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). (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. The particles according to claim 1, wherein the thermal decomposition temperature of said super engineering plastic resin is 330°C or higher.

3. Particles according to claim 1 or 2, wherein the continuous use temperature of said super engineering plastic resin is 140°C or higher.

4. Particles according to any one of claims 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.

5. Particles according to any one of claims 1 to 4, wherein the super engineering plastic resin is at least one selected from the group consisting of fluororesin, liquid crystal polymer, polyaryletherketone and polyethersulfone.

6. Particles according to any one of claims 1 to 5, wherein the super engineering plastic resin is a perfluororesin.

7. Particles according to any one of claims 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.

8. Particles according to any one of claims 1 to 7, 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. Particles according to any one of claims 1 to 8, wherein the filler is a nanofiller.

10. Particles according to any one of claims 1 to 9, wherein the filler is a carbon nanotube.

11. The particles according to any one of claims 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.

12. The particles according to any one of claims 1 to 11, wherein the content of the filler is 0.001 to 30% by mass.

13. The particle according to any one of claims 1 to 12, wherein the group (I) is an oxazoline group and the compound (I) is an oxazoline compound.

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

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

16. The particles according to claim 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.

17. The particles according to any one of claims 14 to 16, wherein the oxazoline group-containing polymer is poly-2-vinyl-2-oxazoline.

18. The particles according to any one of claims 14 to 16, wherein the oxazoline group-containing polymer is a copolymer of 2-isopropenyl-2-oxazoline and an acrylic monomer.

19. Particles according to any one of claims 1 to 18, wherein the content of compound (I) is 0.01 to 50% by mass.

20. Particles according to any one of claims 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 compound (I) is 0.1 to 10% by mass.

21. A composition comprising particles according to any one of claims 1 to 20.

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 or 22.

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 25. The molded article according to claim 23 or 24, wherein the number of particles per unit area is 20 or less.

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

29. The method for producing particles according to any one of claims 26 to 28, wherein in step 3, the particles are collected from the dispersion obtained in step 2 by centrifugation.

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