WO2017199499A1 - Thermoplastic resin composition and curable composition - Google Patents

Thermoplastic resin composition and curable composition Download PDF

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Publication number
WO2017199499A1
WO2017199499A1 PCT/JP2017/006215 JP2017006215W WO2017199499A1 WO 2017199499 A1 WO2017199499 A1 WO 2017199499A1 JP 2017006215 W JP2017006215 W JP 2017006215W WO 2017199499 A1 WO2017199499 A1 WO 2017199499A1
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Prior art keywords
nanodiamond particles
particles
nanodiamond
resin
resin composition
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PCT/JP2017/006215
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French (fr)
Japanese (ja)
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久米篤史
梅本浩一
伊藤久義
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株式会社ダイセル
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

Definitions

  • the present invention relates to a thermoplastic resin composition and a curable composition for obtaining a thermoplastic resin composition.
  • this application claims priority based on Japanese Patent Application No. 2016-100304 dated May 19, 2016, and uses all the contents described in the application.
  • thermoplastic resin materials having high heat resistance such as engineering plastics and super engineering plastics are used as molding materials in various technical fields.
  • a hindered phenol compound may be used as an additive to the resin material.
  • radicals may be generated to induce a decomposition reaction of the resin component.
  • hindered phenolic compounds capture or stabilize radicals to cause such decomposition reactions. It is expected and used for the function to suppress.
  • Such hindered phenol compounds are described, for example, in Patent Documents 1 and 2 below.
  • the radical scavenger which is a hindered phenol compound or other organic compound, often decomposes in a high temperature environment where a high heat resistant resin material such as engineering plastic is used. Therefore, the radical scavenger which is a hindered phenol compound or other organic compound often does not function as an effective additive for improving the heat resistance of the high heat resistant resin material.
  • the present invention has been conceived under the circumstances as described above, and provides a thermoplastic resin composition suitable for realizing high heat resistance, and such a thermoplastic resin composition. It aims at providing the curable composition suitable for obtaining a thing.
  • thermoplastic resin composition includes a polyamideimide resin and nanodiamond particles.
  • the nanodiamond particles include nanodiamond primary particles and / or nanodiamond secondary particles.
  • the nanodiamond primary particles are nanodiamonds having a particle diameter of 10 nm or less.
  • This thermoplastic resin composition contains a polyamide-imide resin (PAI resin) as a resin component as described above.
  • PAI resin has both an amide bond and an imide bond, and the amide bond incorporated in the resin structure brings thermoformability or processability to the resin, and the imide bond incorporated in the resin structure is heat resistant to the resin. Bring.
  • This resin composition containing such a PAI resin as a resin component is suitable for realizing high heat resistance as a thermoplastic resin material.
  • imide bonds also provide mechanical strength in addition to heat resistance
  • amide bonds also provide toughness in addition to processability in the resin.
  • the resin composition can also be used as a high-functional thermoplastic resin material called a super engineering plastic.
  • thermoplastic resin composition includes nanodiamond particles.
  • nanodiamond particles have the effect of further improving the heat resistance of PAI resin having high heat resistance. Specifically, as shown in Examples and Comparative Examples described later, the thermal decomposition of PAI resin is suppressed. The inventors have found that the effect is on nanodiamond particles.
  • the nanodiamond particles can exhibit heat resistance without being decomposed even in a high temperature environment exceeding 400 ° C., for example, and thus form at least one of the surfaces of the nanodiamond primary particles included in the nanodiamond particles.
  • sp 2 structure carbon is generated in the part, that is, at least the ⁇ 111 ⁇ plane by spontaneous transition from the sp 3 structure carbon forming the diamond body.
  • the presence of this sp 2 structure carbon on the nanodiamond surface can contribute to the capture and stabilization of radicals generated in the resin material in a high temperature environment, and therefore, thermal decomposition of the PAI resin due to the action of radicals is suppressed. It is considered a thing.
  • thermoplastic resin composition is suitable for realizing high heat resistance.
  • the PAI resin content of such a thermoplastic resin composition is, for example, 99.99% by mass or less, and preferably 80% by mass or more, more preferably 90% by mass or more, more preferably 92% by mass or more. More preferably, it is 94 mass% or more, More preferably, it is 95 mass% or more.
  • the thermoplastic resin composition has a surface resistivity of 1 ⁇ 10 12 ⁇ / ⁇ or more. According to such a configuration, the present thermoplastic resin composition can be used as a material having high insulation in addition to high heat resistance.
  • a curable composition includes a polyamideimide resin, nanodiamond particles, and a solvent.
  • the solvent is preferably a polar organic solvent. More preferably, the solvent is methanol, ethanol, isopropanol, isobutyl alcohol, ethylene glycol, propylene glycol, glycerin, 2-methoxyethanol, dimethyl sulfoxide, N-methyl-2-pyrrolidone, acetonitrile, N, N-dimethylformamide, N , N-dimethylacetamide, N, N-diethylformamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, hexamethylphosphoramide, dimethylsulfone, ⁇ -butyrolactone, ⁇ -acetyl- ⁇ -butyrolactone, 1 , 3-dimethyl-3,4,5,6-tetrahydro-2 (1H)
  • the 10% pyrolysis temperature of the nanodiamond particles is preferably 400 ° C. or higher, more preferably 420 ° C. or higher, more preferably 450 ° C. or higher, more preferably 500 ° C. or higher, More preferably, it is 520 ° C. or higher.
  • Such a configuration is suitable for realizing high heat resistance in the thermoplastic resin composition.
  • the ratio of the content of nanodiamond particles to the total content of polyamideimide resin and nanodiamond particles is: Preferably it is 0.01 mass% or more, More preferably, it is 0.1 mass% or more, More preferably, it is 1 mass% or more.
  • the proportion is preferably 20% by mass or less, more preferably 10% by mass or less, more preferably 8% by mass or less, and more preferably. Is 6% by mass or less.
  • the nanodiamond particles are preferably detonated nanodiamond particles. According to the detonation method, it is possible to appropriately generate nanodiamond having a primary particle size of 10 nm or less.
  • thermogravimetry about the nano diamond particle used in Example 1 and 2.
  • FIG. 1 is an enlarged schematic view of a resin composition 10 which is a thermoplastic resin composition according to an embodiment of the present invention.
  • the resin composition 10 contains at least a PAI resin 11 that is a polyamide-imide resin and ND particles 12 that are nanodiamond particles.
  • the resin composition 10 can take the form of a resin molding raw material, for example, a pellet, a form that is softened or melted from the form of the resin molding raw material, and a resin molded body formed through a softened / molten state. .
  • the PAI resin 11 contained in the resin composition 10 is a main material for developing functions such as heat resistance in the resin composition 10, and has a glass transition temperature of 250 ° C. or higher, for example.
  • the PAI resin 11 can be synthesized by, for example, an isocyanate method generated from an acid component and an isocyanate component, or an acid chloride method generated from an acid chloride component and an amine component.
  • the acid component contains, for example, trimellitic anhydride as an essential component, and may contain other acidic components other than trimellitic anhydride.
  • other acidic components include tetracarboxylic acid and its anhydride, aliphatic dicarboxylic acid, aromatic dicarboxylic acid, and trifunctional carboxylic acid.
  • the tetracarboxylic acid include pyromellitic acid, biphenyltetracarboxylic acid, biphenylsulfonetetracarboxylic acid, benzophenonetetracarboxylic acid, biphenylethertetracarboxylic acid, and propylene glycol bistrimellitate.
  • Aliphatic dicarboxylic acids include, for example, oxalic acid, adipic acid, malonic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, dicarboxypolybutadiene, dicarboxypoly (acrylonitrile-butadiene), and dicarboxypoly (styrene-butadiene) Is mentioned.
  • aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, diphenylsulfone dicarboxylic acid, diphenyl ether dicarboxylic acid, and naphthalenedicarboxylic acid.
  • the trifunctional carboxylic acid include trimesic acid and cyclohexanetricarboxylic acid.
  • Examples of the isocyanate component used in the above isocyanate method include aromatic diisocyanate, aliphatic diisocyanate, and alicyclic diisocyanate.
  • aromatic diisocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyl ether diisocyanate, and 4,4′-diphenyl sulfone.
  • Examples include diisocyanates, xylylene diisocyanates, and tolidine diisocyanates.
  • Examples of the aliphatic diisocyanate include ethylene diisocyanate, propylene diisocyanate, and hexamethylene diisocyanate.
  • Examples of the alicyclic diisocyanate include 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, isophorone diisocyanate, and 4,4′-dicyclohexylmethane diisocyanate.
  • Examples of the acid chloride component used in the acid chloride method include those having a structure in which the carboxylic acid moiety as a partial structure in the acid component described above with respect to the isocyanate method is replaced by carboxylic acid chloride. Moreover, as an amine component used in said acid chloride method, what has the structure which the site
  • Solvents that can be used in the synthesis of the polyamideimide resin include, for example, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, cyclohexanone, methyl ethyl ketone, ⁇ -Butyrolactone, xylene, and toluene.
  • the content of the PAI resin 11 in the resin composition 10 is, for example, 80 to 99.99% by mass, preferably 90 to 99.99% by mass, more preferably 92 to 99.99% by mass, and more preferably 94 to It is 99.99% by mass, and more preferably 95 to 99.99% by mass.
  • the ND particles 12 contained in the resin composition 10 are components for exhibiting a function as a heat stabilizer or a thermal decomposition inhibitor in the resin composition 10, and are respectively nanodiamond primary particles or nanodiamond secondary particles. Particles.
  • the nanodiamond primary particles are nanodiamonds having a particle diameter of 10 nm or less.
  • the particle diameter D50 (median diameter) of the ND particles 12 in the resin composition 10 is a viewpoint that the surface area per unit mass of the ND particles 12 is sufficiently ensured and the function as a thermal decomposition inhibitor is efficiently exhibited. Is preferably 500 nm or less, more preferably 300 nm or less, more preferably 100 nm or less, and more preferably 80 nm or less.
  • the particle size D50 of the ND particle 12 can be measured by, for example, a dynamic light scattering method.
  • the ND particles 12 contained in the resin composition 10 are, for example, detonation nanodiamond particles (nanodiamond particles generated by detonation).
  • the detonation nanodiamond particles can be obtained, for example, as follows.
  • nano-diamonds are generated by the action of the pressure and energy of the shock wave generated by the explosion, using carbon that is liberated due to partial incomplete combustion of the explosive used.
  • a mixture of trinitrotoluene (TNT) and cyclotrimethylenetrinitroamine, ie hexogen (RDX) can be used.
  • the nanodiamond crude product obtained by the detonation method is likely to contain a metal oxide. This metal oxide is an oxide such as Fe, Co, or Ni derived from a container or the like used in the detonation method.
  • the metal oxide can be dissolved and removed from the nanodiamond crude product (acid treatment).
  • the strong acid used for this acid treatment is preferably a mineral acid, and examples thereof include hydrochloric acid, hydrofluoric acid, sulfuric acid, nitric acid, and aqua regia.
  • the nano-diamond crude product obtained by the detonation method contains graphite. This graphite is derived from carbon that did not form nanodiamond crystals among the carbon released by partial incomplete combustion of the explosive used.
  • graphite can be removed from the nanodiamond crude product (oxidation treatment) by applying a predetermined oxidizing agent in an aqueous solvent, for example.
  • oxidizing agent used in the oxidation treatment include chromic acid, chromic anhydride, dichromic acid, permanganic acid, perchloric acid, and salts thereof, and hydrogen peroxide.
  • Detonation nanodiamonds are aggregated by a very strong interaction between primary particles even after purification through acid treatment and oxidation treatment as described above. It takes the form of adhering bodies (secondary particles).
  • nanodiamonds having a particle size of single-digit nanometers can be obtained.
  • a solvent in which nanodiamond can exhibit solubility is preferable, and examples thereof include water, methanol, ethanol, ethylene glycol, and N-methyl-2-pyrrolidone.
  • the crushing treatment can be performed using, for example, a high shear mixer, a high shear mixer, a homomixer, a ball mill, a bead mill, a high-pressure homogenizer, an ultrasonic homogenizer, or a colloid mill.
  • a nanodiamond dispersion liquid having a predetermined concentration can be obtained by reducing the water content of the suspension in which nanodiamonds are dispersed, as necessary.
  • the nanodiamond powder can be obtained by removing moisture from the suspension in which the nanodiamond is dispersed, if necessary.
  • the 10% pyrolysis temperature of the nanodiamond particles or ND particles 12 thus obtained is preferably 400 ° C. or higher, more preferably 420 ° C. or higher, more preferably 450 ° C. or higher, more preferably 500 ° C. or higher, more preferably Is 520 ° C. or higher.
  • the 10% pyrolysis temperature is a weight reduction from the initial weight (reference weight) when measuring the weight loss while raising the temperature of the object to be measured at 20 ° C./min. This is the temperature at which the rate reaches 10%, and can be measured, for example, by the method described later with respect to the examples.
  • the content of the ND particles 12 is preferably 0.01 to 20% by mass with respect to the total amount of the PAI resin 11 and the ND particles 12 in the resin composition 10. As the content of the ND particles 12 increases, the thermal decomposition inhibiting effect due to the presence of the ND particles 12 tends to increase. However, the lower limit of the content of the ND particles 12 is more preferably 0.1% by mass, More preferably, it is 1 mass%. From the viewpoint of appropriately expressing the resin characteristics of the PAI resin 11 in the resin composition 10, the content of the ND particles 12 may be preferably 20% by mass or less.
  • the upper limit of the content of the ND particles 12 is more preferably 10% by mass, More preferably, it is 8 mass%, More preferably, it is 6 mass%.
  • Resin composition 10 may contain other components in addition to PAI resin 11 and ND particles 12.
  • other components include flame retardants, glass fibers, carbon fibers, antistatic agents, lubricants, and colorants.
  • Resin composition 10 includes polyamideimide resin (PAI resin) 11 as a resin component as described above.
  • the PAI resin 11 has both an amide bond and an imide bond.
  • the amide bond incorporated in the resin structure brings thermoformability or processability to the resin, and the imide bond incorporated in the resin structure is heat resistant to the resin. Bring sex.
  • the resin composition 10 containing such a PAI resin 11 as a resin component is suitable for realizing high heat resistance as a thermoplastic resin material.
  • the imide bond brings mechanical strength to the resin in addition to heat resistance, and the amide bond brings toughness to the resin in addition to processability.
  • Such PAI resin 11 is used as a resin component.
  • the resin composition 10 to be included can also be used as a high-functional thermoplastic resin material called a super engineering plastic.
  • the resin composition 10 includes nanodiamond particles (ND particles) 12 as described above.
  • the ND particles 12 have the effect of further improving the heat resistance of the PAI resin 11 having high heat resistance.
  • the PAI resin 11 is thermally decomposed.
  • the present inventors have found that the ND particles 12 have an inhibitory effect.
  • the ND particles 12 can exhibit heat resistance even in a high temperature environment exceeding 400 ° C., for example.
  • the ND particles 12 form at least a part of the surface of the nanodiamond primary particles that form the ND particles 12 or are included in the ND particles 12, that is, at least It is assumed that sp 2 structure carbon is generated on the ⁇ 111 ⁇ plane by spontaneous transition from the sp 3 structure carbon forming the diamond body.
  • the presence of this sp 2 structure carbon on the surface of the nanodiamond can contribute to the capture and stabilization of radicals generated in the resin material in a high temperature environment, and therefore, thermal decomposition of the PAI resin 11 due to the action of radicals is suppressed. It is thought that.
  • the resin composition 10 of the present embodiment is suitable for realizing high heat resistance.
  • the resin composition 10 can be used, for example, as a resin material for forming a sliding material for an engine bearing such as an automobile.
  • the surface resistivity of the resin composition 10 is preferably 1 ⁇ 10 12 ⁇ / ⁇ or more, more preferably 5 ⁇ 10 12 ⁇ / ⁇ or more, and more preferably 1 ⁇ 10 13 ⁇ / ⁇ or more. According to such a configuration, the resin composition 10 can be used as a material having high insulation in addition to high heat resistance.
  • the resin composition 10 can be produced, for example, by applying a curable composition containing the above-described PAI resin 11, the above-described ND particles 12, and a solvent to a substrate and then drying the substrate. is there.
  • a solvent contained in the curable composition for example, a polar organic solvent in which the PAI resin 11 exhibits solubility and the ND particles 12 exhibit solubility is used in the present embodiment.
  • polar organic solvents examples include methanol, ethanol, isopropanol, isobutyl alcohol, ethylene glycol, propylene glycol, glycerin, 2-methoxyethanol, dimethyl sulfoxide, N-methyl-2-pyrrolidone, acetonitrile, N, N- Dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, hexamethylphosphoramide, dimethylsulfone, ⁇ -butyrolactone, ⁇ -acetyl- ⁇ -Butyrolactone, 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone, 1,3-dimethyl-2-imidazolidinone, tetramethylurea, cyclohexanone, tetrahydrofurfuryl acetate, and And propylene
  • the solvent one type of solvent may be used, or two or more types of solvents may be used. From the viewpoint that both the PAI resin 11 and the ND particles 12 have relatively high solubility, N-methyl-2-pyrrolidone is preferable as the solvent.
  • preparation of said curable composition can be performed by mixing the solution containing PAI resin 11 and the solution containing ND particle
  • the solution containing the PAI resin 11 for example, an organic solvent solution containing the PAI resin 11 synthesized by the above-described isocyanate method or acid chloride method, or a solvent component replacement operation by solvent replacement of the solution is used.
  • the passed organic solvent solution can be used.
  • an organic solvent solution obtained by subjecting the aqueous dispersion in which the ND particles 12 are dispersed to a solvent replacement operation from water to an organic solvent can be used.
  • the content of the PAI resin 11 is, for example, 5 to 20% by mass, and the content of the ND particles 12 is The total amount of ND particles 12 is preferably 0.01 to 20% by mass.
  • the thermal decomposition inhibiting effect due to the presence of the ND particles 12 tends to increase in the resin composition 10 to be formed, and the lower limit of the content of the ND particles 12 is, More preferably, it is 0.1 mass%, More preferably, it is 1 mass%.
  • the content of the ND particles 12 may be preferably 20% by mass or less.
  • the upper limit of the content of the ND particles 12 is more preferably 10 It is 8 mass%, More preferably, it is 8 mass%, More preferably, it is 6 mass%.
  • a nanodiamond aqueous dispersion (trade name “Vox D”, solid content or nanodiamond concentration is 5 mass%, aqueous solvent, particle size D50 is 5 nm, zeta potential at pH 9 is ⁇ 55 mV, manufactured by Carbodeon. ) was replaced with N-methyl-2-pyrrolidone (NMP, boiling point 202 ° C.). Specifically, 60 g of NMP (concentration 99.5% by mass, manufactured by Kishida Chemical Co., Ltd.) is added to 2.3 g of the nanodiamond aqueous dispersion and mixed, and the mixture is heated and decompressed using an evaporator. Placed under conditions.
  • NMP N-methyl-2-pyrrolidone
  • the mixture is heated with a stirrer under a reduced pressure of 1.5 kPa from an initial temperature of 45 ° C. to 80 ° C. over 25 minutes, and then under reduced pressure of 1.5 kPa. At 80 ° C. for about 20 minutes.
  • an NMP dispersion of nanodiamond particles was prepared.
  • the nanodiamond NMP dispersion had a nanodiamond solid content concentration of 2.0% by mass.
  • the particle size of the nanodiamond particles contained in this dispersion was measured by a dynamic light scattering method using an apparatus (trade name “Zetasizer Nano ZS”) manufactured by Spectris Co., Ltd. ) Was 12.4 nm.
  • the nanodiamond NMP dispersion prepared as described above and a polyamideimide resin-containing solution (trade name “Bilomax® HR-11NN”, solid content concentration or polyamideimide resin concentration is 15% by mass, NMP solvent, manufactured by Toyobo Co., Ltd.).
  • a polyamideimide resin-containing solution trade name “Bilomax® HR-11NN”, solid content concentration or polyamideimide resin concentration is 15% by mass, NMP solvent, manufactured by Toyobo Co., Ltd.
  • the above-mentioned nanodiamond NMP dispersion is added thereto by a dropping operation, so that the nanodiamond content with respect to 95 parts by mass of the polyamideimide resin is 5 parts by mass.
  • the polyamideimide resin-containing solution and the nanodiamond NMP dispersion were mixed.
  • the curable composition of Example 1 containing polyamideimide resin, nanodiamond particles, and NMP as a solvent was produced.
  • thermoplastic resin composition A thermoplastic resin composition was produced from the curable composition of Example 1 produced as described above. First, using a squeegee, the curable composition was applied on a glass plate with a predetermined thickness. And the said glass plate in which the coating film of the curable composition was formed was put in the muffle furnace, and it baked in nitrogen atmosphere. Specifically, first, heating was performed at 130 ° C. for 10 minutes, then the temperature was increased from 130 ° C. to 300 ° C. over 60 minutes, and then heating was performed at 300 ° C. for 60 minutes.
  • thermoplastic resin composition of Example 1 containing a polyamideimide resin and nanodiamond particles that is, a resin film of Example 1 in which a polyamideimide resin and nanodiamond particles were combined was prepared. .
  • nanodiamond content is 5 mass% and thickness is 20 micrometers.
  • thermogravimetric measuring device (trade name “TG-DTA6300”, manufactured by SII Nano Technology Co., Ltd.), 460 ° C. in an air atmosphere.
  • the weight loss during the holding was measured.
  • the weight of the measurement object when held at 460 ° C. for 10 minutes was defined as the reference weight (initial weight).
  • the result is represented by a line E1 in the graph of FIG.
  • the horizontal axis represents the time (minutes) that is the retention time of the measurement target at 460 ° C.
  • the vertical axis represents TG (%) as the weight change rate from the reference weight.
  • maintaining at 410 degreeC in an air atmosphere using a thermogravimetry apparatus brand name "TG-DTA6300", SII nanotechnology Co., Ltd. make.
  • the amount of decrease was measured.
  • the weight of the measurement object when held at 410 ° C. for 10 minutes was defined as the reference weight (initial weight).
  • the result is represented by a line E1 in the graph of FIG.
  • the horizontal axis represents the time (minutes) that is the holding time of the measurement target at 410 ° C.
  • the vertical axis represents TG (%) as the weight change rate from the reference weight.
  • the weight change rate was ⁇ 3 It was .76%, that is, the weight reduction rate was 3.76%.
  • Example 2 (Preparation of curable composition) Nanodiamond aqueous dispersion prepared separately in place of the nanodiamond aqueous dispersion used in Example 1 (solid content concentration or nanodiamond concentration is 1.08% by mass, aqueous solvent, particle size D50 is 6.04 nm, pH 6) The water as the solvent of the nanodiamond aqueous dispersion was replaced with NMP (solvent replacement step) in the same manner as in the solvent replacement step of Example 1 except that the zeta potential of -42 mV, manufactured by Daicel Corporation) was used. The nanodiamond NMP dispersion thus obtained had a nanodiamond solid content concentration of 2.0% by mass.
  • NMP solvent replacement step
  • the particle diameter of the nanodiamond particles contained in this dispersion was measured by the dynamic light scattering method in the same manner as in Example 1, the particle diameter D50 (median diameter) was 6.83 nm.
  • the obtained nanodiamond NMP dispersion was mixed with a polyamideimide resin-containing solution (trade name “Vilomax HR-11NN”, manufactured by Toyobo Co., Ltd.).
  • a polyamideimide resin-containing solution trade name “Vilomax HR-11NN”, manufactured by Toyobo Co., Ltd.
  • the above-mentioned nanodiamond NMP dispersion is added thereto by a dropping operation, so that the nanodiamond content with respect to 95 parts by mass of the polyamideimide resin is 5 parts by mass.
  • the polyamideimide resin-containing solution and the nanodiamond NMP dispersion were mixed.
  • the curable composition of Example 2 containing polyamideimide resin, nanodiamond particles, and NMP as a solvent was
  • thermoplastic resin composition i.e., the polyamideimide resin and the nanomaterial, was used in the same manner as in Example 1 except that the curable composition of Example 2 was used instead of the curable composition of Example 1.
  • a resin film of Example 2 in which diamond particles were combined was produced. About this resin film, nanodiamond content is 5 mass% and thickness is 20 micrometers.
  • Comparative Example 1 [Preparation of thermoplastic resin composition] Comparative Example 1 is the same as Example 1 except that a polyamideimide resin-containing solution (trade name “Vilomax HR-11NN”, manufactured by Toyobo Co., Ltd.) is used instead of the curable composition of Example 1.
  • a thermoplastic resin composition that is, a polyamideimide resin film of Comparative Example 1 was produced. The resin film has a thickness of 20 ⁇ m.
  • the polyamideimide resin film of Comparative Example 1 is held at 410 ° C. in an air atmosphere using a thermogravimetric measurement device (trade name “TG-DTA6300”) in the same manner as the resin film of Example 1. The amount of weight loss during was measured. The result is represented by a line C1 in the graph of FIG.
  • TG-DTA6300 thermogravimetric measurement device
  • nanodiamond contained in the nanodiamond aqueous dispersion used in each of Examples 1 and 2 was measured for its 10% thermal decomposition temperature. Specifically, first, nanodiamond powder was obtained from the nanodiamond aqueous dispersion by heat drying using a sand bath. Next, the obtained nanodiamond powder was subjected to thermogravimetric measurement using a thermogravimetric measurement device (trade name “TG-DTA6300”, manufactured by SII Nanotechnology Inc.). In this measurement, the measurement target is held at 200 ° C. for 10 minutes in a nitrogen atmosphere to sufficiently suppress the influence of the contained moisture on the measurement result, and then the rate of temperature increase from 200 ° C.
  • TG-DTA6300 thermogravimetric measurement device
  • the weight loss during the process of increasing the temperature at 20 ° C./min was measured.
  • the weight of the object to be measured when it was held at 200 ° C. for 10 minutes was defined as the reference weight (initial weight).
  • the result is shown in the graph of FIG.
  • the horizontal axis represents temperature (° C.)
  • the vertical axis represents TG (%) as a weight change rate from the reference weight (initial weight).
  • the measurement result relating to the nanodiamond particles used in Example 1 is represented by a line E1 ′
  • the measurement result relating to the nanodiamond particles used in Example 2 is represented by a line E2 ′.
  • the 10% pyrolysis temperature of the nanodiamond particles used in Example 1 was 525.4 ° C.
  • the 10% pyrolysis temperature of the nanodiamond particles used in Example 2 was 40.8 ° C.
  • a thermogravimetric measuring device (trade name “TG-DTA6300”, SII Using Nanotechnology Co., Ltd.), the amount of weight loss in the process of raising the temperature from 30 ° C. to 550 ° C. at a rate of temperature increase of 20 ° C./min under an air atmosphere was measured.
  • The% thermal decomposition temperature was 499 ° C.
  • the resin film as the thermoplastic resin composition of Examples 1 and 2 in which the nanodiamond particles are dispersed is the polyamideimide resin film of Comparative Example 1 that does not contain nanodiamond particles. It can be seen that thermal decomposition is suppressed, that is, heat resistance is high. Further, from the results shown in the graph of FIG. 2, the resin film which is the thermoplastic resin composition of Example 1 in which nanodiamond particles having a relatively high 10% pyrolysis temperature are dispersed therein has a 10% pyrolysis temperature. It can be seen that the thermal decomposition is suppressed, that is, the heat resistance is higher than that of the resin film which is the thermoplastic resin composition of Example 2 in which relatively low nano-diamond particles are dispersed.
  • thermoplastic resin composition comprising a polyamideimide resin and nanodiamond particles.
  • Appendix 2 The thermoplastic resin composition according to Appendix 1, wherein the nanodiamond particles have a 10% thermal decomposition temperature of 400 ° C. or higher.
  • Appendix 3 The thermoplastic resin composition according to Appendix 1, wherein the nanodiamond particles have a 10% thermal decomposition temperature of 420 ° C. or higher.
  • Appendix 4 The thermoplastic resin composition according to Appendix 1, wherein the nanodiamond particles have a 10% thermal decomposition temperature of 450 ° C. or higher.
  • thermoplastic resin composition according to Appendix 1, wherein the nanodiamond particles have a 10% thermal decomposition temperature of 500 ° C. or higher.
  • thermoplastic resin composition according to Appendix 1 The thermoplastic resin composition according to Appendix 1, wherein the nanodiamond particles have a 10% thermal decomposition temperature of 520 ° C. or higher.
  • Appendix 7 The heat according to any one of appendices 1 to 6, wherein a ratio of the content of the nanodiamond particles to the total content of the polyamideimide resin and the nanodiamond particles is 0.01% by mass or more. Plastic resin composition.
  • thermoplastic resin according to any one of appendices 1 to 9, wherein the ratio of the content of the nanodiamond particles to the total content of the polyamideimide resin and the nanodiamond particles is 20% by mass or less.
  • Composition [Appendix 11] The thermoplastic resin according to any one of Appendixes 1 to 9, wherein a ratio of the content of the nanodiamond particles to a total content of the polyamideimide resin and the nanodiamond particles is 10% by mass or less. Composition.
  • Appendix 13 The thermoplastic resin according to any one of appendices 1 to 9, wherein a ratio of the content of the nanodiamond particles to the total content of the polyamideimide resin and the nanodiamond particles is 6% by mass or less.
  • Appendix 14 The thermoplastic resin composition according to any one of Appendixes 1 to 13, wherein the nanodiamond particles are detonation nanodiamond particles.
  • Subsupplementary Note 16 The thermoplastic resin composition according to any one of Supplementary notes 1 to 14, wherein the content of the polyamideimide resin is 90% by mass or more.
  • Appendix 17 The thermoplastic resin composition according to any one of Appendixes 1 to 14, wherein the content of the polyamideimide resin is 92% by mass or more.
  • Appendix 18 The thermoplastic resin composition according to any one of Appendixes 1 to 14, wherein the content of the polyamideimide resin is 94% by mass or more.
  • thermoplastic resin composition according to any one of appendices 1 to 14, wherein the content of the polyamideimide resin is 95% by mass or more.
  • Appendix 20 The thermoplastic resin composition according to any one of Appendixes 1 to 19, wherein the surface resistivity is 1 ⁇ 10 12 ⁇ / ⁇ or more.
  • Appendix 21 A curable composition comprising a polyamideimide resin, nanodiamond particles, and a solvent.
  • nanodiamond particles have a 10% thermal decomposition temperature of 400 ° C. or higher.
  • [Supplementary note 27] The curing according to any one of Supplementary notes 22 to 26, wherein a ratio of the content of the nanodiamond particles to the total content of the polyamideimide resin and the nanodiamond particles is 0.01% by mass or more. Sex composition.
  • [Appendix 28] The curing according to any one of appendices 22 to 26, wherein the ratio of the content of the nanodiamond particles to the total content of the polyamideimide resin and the nanodiamond particles is 0.1% by mass or more. Sex composition.
  • [Appendix 33] The curable composition according to any one of appendices 21 to 29, wherein the ratio of the content of the nanodiamond particles to the total content of the polyamideimide resin and the nanodiamond particles is 6% by mass or less. object.
  • [Appendix 34] The curable composition according to any one of appendices 21 to 33, wherein the nanodiamond particles are detonation nanodiamond particles.
  • [Appendix 35] The curable composition according to any one of Appendixes 21 to 34, wherein the solvent is a polar organic solvent.
  • the polar organic solvent is methanol, ethanol, isopropanol, isobutyl alcohol, ethylene glycol, propylene glycol, glycerin, 2-methoxyethanol, dimethyl sulfoxide, N-methyl-2-pyrrolidone, acetonitrile, N, N-dimethyl.
  • Resin composition thermoplastic resin composition
  • PAI resin polyamideimide resin
  • ND particles nanomond particles

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Abstract

A resin composition (10) as this thermoplastic resin composition includes a polyamide-imide resin (11) and nanodiamond particles (12). The 10% thermal decomposition temperature of the nanodiamond particles (12) is, for example, 400°C or higher. Such a thermoplastic resin composition is suitable for realizing high heat resistance. This curable composition includes a polyamide-imide resin (11), nanodiamond particles (12), and a solvent. Such a curable composition is appropriate for being able to obtain a thermoplastic resin composition suitable for realizing high heat resistance.

Description

熱可塑性樹脂組成物および硬化性組成物Thermoplastic resin composition and curable composition
　本発明は、熱可塑性の樹脂組成物、および、熱可塑性樹脂組成物を得るための硬化性組成物に関する。また、本願は、２０１６年５月１９日付の日本出願 特願２０１６－１００３０４号に基づく優先権を主張し、当該出願に記載されている全ての内容を援用するものである。 The present invention relates to a thermoplastic resin composition and a curable composition for obtaining a thermoplastic resin composition. In addition, this application claims priority based on Japanese Patent Application No. 2016-100304 dated May 19, 2016, and uses all the contents described in the application.
　近年、エンジニアリングプラスチックやスーパーエンジニアリングプラスチックなど、高い耐熱性を有する熱可塑性樹脂材料が、様々な技術分野において例えば成形材料として用いられている。 In recent years, thermoplastic resin materials having high heat resistance such as engineering plastics and super engineering plastics are used as molding materials in various technical fields.
　一方、樹脂材料の耐熱性を向上させる目的で、樹脂材料への添加剤としてヒンダードフェノール系化合物が用いられることがある。高温環境下におかれた樹脂材料中では、ラジカルが発生して樹脂成分の分解反応を誘発する場合があるところ、ヒンダードフェノール系化合物は、ラジカルを捕捉ないし安定化させてそのような分解反応を抑制する機能を期待されて、用いられる。このようなヒンダードフェノール系化合物については、例えば下記の特許文献１,２に記載されている。 On the other hand, for the purpose of improving the heat resistance of the resin material, a hindered phenol compound may be used as an additive to the resin material. In resin materials placed in a high-temperature environment, radicals may be generated to induce a decomposition reaction of the resin component. However, hindered phenolic compounds capture or stabilize radicals to cause such decomposition reactions. It is expected and used for the function to suppress. Such hindered phenol compounds are described, for example, in Patent Documents 1 and 2 below.
特開２００２－３３２３０６号公報JP 2002-332306 A 特開２０１１－２０８１５７号公報JP 2011-208157 A
　ヒンダードフェノール系化合物その他の有機化合物たるラジカル捕捉剤は、エンジニアリングプラスチック等の高耐熱性樹脂材料が使用されることとなる高温環境下では分解してしまう場合が多い。したがって、ヒンダードフェノール系化合物その他の有機化合物たるラジカル捕捉剤は、当該高耐熱性樹脂材料にとってその耐熱性を向上させる有効な添加剤として機能しない場合が多い。 The radical scavenger, which is a hindered phenol compound or other organic compound, often decomposes in a high temperature environment where a high heat resistant resin material such as engineering plastic is used. Therefore, the radical scavenger which is a hindered phenol compound or other organic compound often does not function as an effective additive for improving the heat resistance of the high heat resistant resin material.
　本発明は、以上のような事情の下で考え出されたものであって、高い耐熱性を実現するのに適した熱可塑性樹脂組成物を提供すること、および、そのような熱可塑性樹脂組成物を得るのに適した硬化性組成物を提供することを、目的とする。 The present invention has been conceived under the circumstances as described above, and provides a thermoplastic resin composition suitable for realizing high heat resistance, and such a thermoplastic resin composition. It aims at providing the curable composition suitable for obtaining a thing.
　本発明の第１の側面によると、熱可塑性樹脂組成物が提供される。この熱可塑性樹脂組成物は、ポリアミドイミド樹脂およびナノダイヤモンド粒子を含む。本発明において、ナノダイヤモンド粒子は、ナノダイヤモンド一次粒子および／またはナノダイヤモンド二次粒子を含む。本発明において、ナノダイヤモンド一次粒子とは、粒径１０ｎｍ以下のナノダイヤモンドをいうものとする。 According to the first aspect of the present invention, a thermoplastic resin composition is provided. The thermoplastic resin composition includes a polyamideimide resin and nanodiamond particles. In the present invention, the nanodiamond particles include nanodiamond primary particles and / or nanodiamond secondary particles. In the present invention, the nanodiamond primary particles are nanodiamonds having a particle diameter of 10 nm or less.
　本熱可塑性樹脂組成物は、樹脂成分として、上述のようにポリアミドイミド樹脂（ＰＡＩ樹脂）を含む。ＰＡＩ樹脂は、アミド結合とイミド結合とを合わせもつところ、樹脂構造に組み込まれたアミド結合は樹脂に熱成形性ないし加工性をもたらし、且つ、樹脂構造に組み込まれたイミド結合は樹脂に耐熱性をもたらす。このようなＰＡＩ樹脂を樹脂成分として含む本樹脂組成物は、熱可塑性樹脂材料として高い耐熱性を実現するのに適する。また、ＰＡＩ樹脂においてイミド結合は樹脂に耐熱性に加えて機械的強度をももたらし且つアミド結合は樹脂に加工性に加えて強靭性をももたらすところ、このようなＰＡＩ樹脂を樹脂成分として含む本樹脂組成物は、スーパーエンジニアリングプラスチックと呼称される高機能熱可塑性樹脂材料として用いることも可能である。 This thermoplastic resin composition contains a polyamide-imide resin (PAI resin) as a resin component as described above. PAI resin has both an amide bond and an imide bond, and the amide bond incorporated in the resin structure brings thermoformability or processability to the resin, and the imide bond incorporated in the resin structure is heat resistant to the resin. Bring. This resin composition containing such a PAI resin as a resin component is suitable for realizing high heat resistance as a thermoplastic resin material. In PAI resins, imide bonds also provide mechanical strength in addition to heat resistance, and amide bonds also provide toughness in addition to processability in the resin. A book containing such a PAI resin as a resin component. The resin composition can also be used as a high-functional thermoplastic resin material called a super engineering plastic.
　加えて、本熱可塑性樹脂組成物は、ナノダイヤモンド粒子を含む。上述のように耐熱性の高いＰＡＩ樹脂の耐熱性を更に向上させる効果がナノダイヤモンド粒子にあること、具体的には、後記の実施例および比較例をもって示すようにＰＡＩ樹脂の熱分解を抑制する効果がナノダイヤモンド粒子にあることを、本発明者らは見出した。ナノダイヤモンド粒子は例えば４００℃を超える高温環境下でも分解せずに耐熱性を示し得るものであるところ、そのようなナノダイヤモンド粒子をなすか或いはこれに含まれるナノダイヤモンド一次粒子の表面の少なくとも一部、即ち少なくとも｛１１１｝面には、ダイヤモンド本体をなすｓｐ3構造炭素からの自発転移によってｓｐ2構造炭素が生じているものと想定される。ナノダイヤモンド表面におけるこのｓｐ2構造炭素の存在が、高温環境下の樹脂材料中に発生するラジカルの補足や安定化に寄与し得て、従って、ラジカルの作用によるＰＡＩ樹脂の熱分解が抑制されるものと考えられる。 In addition, the thermoplastic resin composition includes nanodiamond particles. As described above, nanodiamond particles have the effect of further improving the heat resistance of PAI resin having high heat resistance. Specifically, as shown in Examples and Comparative Examples described later, the thermal decomposition of PAI resin is suppressed. The inventors have found that the effect is on nanodiamond particles. The nanodiamond particles can exhibit heat resistance without being decomposed even in a high temperature environment exceeding 400 ° C., for example, and thus form at least one of the surfaces of the nanodiamond primary particles included in the nanodiamond particles. It is assumed that sp 2 structure carbon is generated in the part, that is, at least the {111} plane by spontaneous transition from the sp 3 structure carbon forming the diamond body. The presence of this sp 2 structure carbon on the nanodiamond surface can contribute to the capture and stabilization of radicals generated in the resin material in a high temperature environment, and therefore, thermal decomposition of the PAI resin due to the action of radicals is suppressed. It is considered a thing.
　以上のように、本熱可塑性樹脂組成物は、高い耐熱性を実現するのに適するのである。このような本熱可塑性樹脂組成物のＰＡＩ樹脂含有量は、例えば９９.９９質量％以下であり、且つ、好ましくは８０質量％以上、より好ましくは９０質量％以上、より好ましくは９２質量％以上、より好ましくは９４質量％以上、より好ましくは９５質量％以上である。 As described above, the present thermoplastic resin composition is suitable for realizing high heat resistance. The PAI resin content of such a thermoplastic resin composition is, for example, 99.99% by mass or less, and preferably 80% by mass or more, more preferably 90% by mass or more, more preferably 92% by mass or more. More preferably, it is 94 mass% or more, More preferably, it is 95 mass% or more.
　好ましくは、本熱可塑性樹脂組成物の表面抵抗率は１×１０12Ω/□以上である。このような構成によると、本熱可塑性樹脂組成物について、高い耐熱性に加えて高い絶縁性を有する材料として用いることが可能となる。 Preferably, the thermoplastic resin composition has a surface resistivity of 1 × 10 12 Ω / □ or more. According to such a configuration, the present thermoplastic resin composition can be used as a material having high insulation in addition to high heat resistance.
　本発明の第２の側面によると、硬化性組成物が提供される。この硬化性組成物は、ポリアミドイミド樹脂と、ナノダイヤモンド粒子と、溶媒とを含む。溶媒は、好ましくは極性有機溶媒である。溶媒は、より好ましくは、メタノール、エタノール、イソプロパノール、イソブチルアルコール、エチレングリコール、プロピレングリコール、グリセリン、２-メトキシエタノール、ジメチルスルホキシド、Ｎ-メチル-２-ピロリドン、アセトニトリル、Ｎ,Ｎ-ジメチルホルムアミド、Ｎ,Ｎ-ジメチルアセトアミド、Ｎ,Ｎ-ジエチルホルムアミド、Ｎ,Ｎ-ジエチルアセトアミド、Ｎ,Ｎ-ジメチルメトキシアセトアミド、ヘキサメチルホスホルアミド、ジメチルスルホン、γ-ブチロラクトン、α-アセチル-γ-ブチロラクトン、１,３-ジメチル-３,４,５,６-テトラヒドロ-２(１Ｈ)-ピリミジノン、１,３-ジメチル-２-イミダゾリジノン、テトラメチル尿素、シクロヘキサノン、酢酸テトラヒドロフルフリル、および炭酸プロピレンからなる群より選択される少なくとも一つを含む。このような構成の硬化性組成物は、上述の第１の側面に係る熱可塑性樹脂組成物を形成するためのいわゆるワニスとして使用することができる。したがって、本硬化性組成物は、高い耐熱性を実現するのに適した熱可塑性樹脂組成物を得るうえで好適である。 According to a second aspect of the present invention, a curable composition is provided. The curable composition includes a polyamideimide resin, nanodiamond particles, and a solvent. The solvent is preferably a polar organic solvent. More preferably, the solvent is methanol, ethanol, isopropanol, isobutyl alcohol, ethylene glycol, propylene glycol, glycerin, 2-methoxyethanol, dimethyl sulfoxide, N-methyl-2-pyrrolidone, acetonitrile, N, N-dimethylformamide, N , N-dimethylacetamide, N, N-diethylformamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, hexamethylphosphoramide, dimethylsulfone, γ-butyrolactone, α-acetyl-γ-butyrolactone, 1 , 3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone, 1,3-dimethyl-2-imidazolidinone, tetramethylurea, cyclohexanone, tetrahydrofurfuryl acetate, and propylene carbonate Selected from group Even without including the one. The curable composition having such a configuration can be used as a so-called varnish for forming the thermoplastic resin composition according to the first aspect described above. Therefore, this curable composition is suitable for obtaining a thermoplastic resin composition suitable for realizing high heat resistance.
　本発明の第１および第２の側面において、ナノダイヤモンド粒子の１０％熱分解温度は、好ましくは４００℃以上、より好ましくは４２０℃以上、より好ましくは４５０℃以上、より好ましくは５００℃以上、より好ましくは５２０℃以上である。このような構成は、本熱可塑性樹脂組成物において高い耐熱性を実現するうえで好適である。 In the first and second aspects of the present invention, the 10% pyrolysis temperature of the nanodiamond particles is preferably 400 ° C. or higher, more preferably 420 ° C. or higher, more preferably 450 ° C. or higher, more preferably 500 ° C. or higher, More preferably, it is 520 ° C. or higher. Such a configuration is suitable for realizing high heat resistance in the thermoplastic resin composition.
　本発明の第１の側面に係る熱可塑性樹脂組成物および第２の側面に係る硬化性組成物において、ポリアミドイミド樹脂とナノダイヤモンド粒子との合計含有量に対するナノダイヤモンド粒子の含有量の割合は、好ましくは０.０１質量％以上、より好ましくは０.１質量％以上、より好ましくは１質量％以上である。ナノダイヤモンド粒子の含有量が多いほど、ナノダイヤモンド粒子の存在に起因する上記の熱分解抑制効果は大きい傾向にある。熱可塑性樹脂組成物において絶縁性等の機能を適切に発現させるという観点からは、当該割合は、好ましくは２０質量％以下、より好ましくは１０質量％以下、より好ましくは８質量％以下、より好ましくは６質量％以下である。 In the thermoplastic resin composition according to the first aspect of the present invention and the curable composition according to the second aspect, the ratio of the content of nanodiamond particles to the total content of polyamideimide resin and nanodiamond particles is: Preferably it is 0.01 mass% or more, More preferably, it is 0.1 mass% or more, More preferably, it is 1 mass% or more. The higher the content of nanodiamond particles, the greater the effect of suppressing thermal decomposition due to the presence of nanodiamond particles. From the viewpoint of appropriately expressing functions such as insulation in the thermoplastic resin composition, the proportion is preferably 20% by mass or less, more preferably 10% by mass or less, more preferably 8% by mass or less, and more preferably. Is 6% by mass or less.
　本発明の第１および第２の側面において、ナノダイヤモンド粒子は、好ましくは爆轟法ナノダイヤモンド粒子である。爆轟法によると、一次粒子の粒径が１０ｎｍ以下のナノダイヤモンドを適切に生じさせることが可能である。 In the first and second aspects of the present invention, the nanodiamond particles are preferably detonated nanodiamond particles. According to the detonation method, it is possible to appropriately generate nanodiamond having a primary particle size of 10 nm or less.
本発明の一の実施形態に係る熱可塑性樹脂組成物の拡大模式図である。It is an expansion schematic diagram of the thermoplastic resin composition which concerns on one Embodiment of this invention. 実施例１,２および比較例１の樹脂組成物についての一の熱重量測定の結果を表すグラフである。It is a graph showing the result of one thermogravimetric measurement about the resin composition of Example 1, 2 and the comparative example 1. FIG. 実施例１および比較例１の樹脂組成物についての一の熱重量測定の結果を表すグラフである。It is a graph showing the result of one thermogravimetric measurement about the resin composition of Example 1 and Comparative Example 1. 実施例１,２で使用したナノダイヤモンド粒子についての熱重量測定の結果を表すグラフである。It is a graph showing the result of the thermogravimetry about the nano diamond particle used in Example 1 and 2.
　図１は、本発明の一の実施形態に係る熱可塑性樹脂組成物たる樹脂組成物１０の拡大模式図である。樹脂組成物１０は、ポリアミドイミド樹脂たるＰＡＩ樹脂１１と、ナノダイヤモンド粒子たるＮＤ粒子１２とを少なくとも含有する。樹脂組成物１０は、樹脂成形原料たる例えばペレットの形態、樹脂成形原料の形態から軟化または溶融した状態にある形態、および、軟化・溶融状態を経て形成された樹脂成形体の形態を、とり得る。 FIG. 1 is an enlarged schematic view of a resin composition 10 which is a thermoplastic resin composition according to an embodiment of the present invention. The resin composition 10 contains at least a PAI resin 11 that is a polyamide-imide resin and ND particles 12 that are nanodiamond particles. The resin composition 10 can take the form of a resin molding raw material, for example, a pellet, a form that is softened or melted from the form of the resin molding raw material, and a resin molded body formed through a softened / molten state. .
　樹脂組成物１０に含有されるＰＡＩ樹脂１１は、樹脂組成物１０において耐熱性等の機能を発現させるための主材であり、例えば２５０℃以上のガラス転移温度を有する。ＰＡＩ樹脂１１については、例えば、酸成分とイソシアネート成分とから生成するイソシアネート法や、酸クロライド成分とアミン成分とから生成する酸クロライド法によって、合成することができる。 The PAI resin 11 contained in the resin composition 10 is a main material for developing functions such as heat resistance in the resin composition 10, and has a glass transition temperature of 250 ° C. or higher, for example. The PAI resin 11 can be synthesized by, for example, an isocyanate method generated from an acid component and an isocyanate component, or an acid chloride method generated from an acid chloride component and an amine component.
　上記のイソシアネート法において、酸成分は、例えばトリメリット酸無水物を必須成分として含み、トリメリット酸無水物以外の他の酸性分を含んでもよい。そのような他の酸性分としては、例えば、テトラカルボン酸およびその無水物、脂肪族ジカルボン酸、芳香族ジカルボン酸、並びに三官能カルボン酸が挙げられる。テトラカルボン酸としては、例えば、ピロメリット酸、ビフェニルテトラカルボン酸、ビフェニルスルホンテトラカルボン酸、ベンゾフェノンテトラカルボン酸、ビフェニルエーテルテトラカルボン酸、およびプロピレングリコールビストリメリテートが挙げられる。脂肪族ジカルボン酸としては、例えば、シュウ酸、アジピン酸、マロン酸、セバシン酸、アゼライン酸、ドデカンジカルボン酸、ジカルボキシポリブタジエン、ジカルボキシポリ(アクリロニトリル-ブタジエン）、およびジカルボキシポリ(スチレン-ブタジエン)が挙げられる。芳香族ジカルボン酸としては、例えば、テレフタル酸、イソフタル酸、ジフェニルスルホンジカルボン酸、ジフェニルエーテルジカルボン酸、およびナフタレンジカルボン酸が挙げられる。三官能カルボン酸としては、例えば、トリメシン酸およびシクロヘキサントリカルボン酸が挙げられる。 In the above isocyanate method, the acid component contains, for example, trimellitic anhydride as an essential component, and may contain other acidic components other than trimellitic anhydride. Examples of such other acidic components include tetracarboxylic acid and its anhydride, aliphatic dicarboxylic acid, aromatic dicarboxylic acid, and trifunctional carboxylic acid. Examples of the tetracarboxylic acid include pyromellitic acid, biphenyltetracarboxylic acid, biphenylsulfonetetracarboxylic acid, benzophenonetetracarboxylic acid, biphenylethertetracarboxylic acid, and propylene glycol bistrimellitate. Aliphatic dicarboxylic acids include, for example, oxalic acid, adipic acid, malonic acid, sebacic acid, azelaic acid, dodecanedicarboxylic acid, dicarboxypolybutadiene, dicarboxypoly (acrylonitrile-butadiene), and dicarboxypoly (styrene-butadiene) Is mentioned. Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, diphenylsulfone dicarboxylic acid, diphenyl ether dicarboxylic acid, and naphthalenedicarboxylic acid. Examples of the trifunctional carboxylic acid include trimesic acid and cyclohexanetricarboxylic acid.
　上記のイソシアネート法において用いられるイソシアネート成分としては、例えば、芳香族ジイソシアネート、脂肪族ジイソシアネート、および脂環式ジイソシアネートが挙げられる。芳香族ジイソシアネートとしては、例えば、２,４-トリレンジイソシアネート、２,６-トリレンジイソシアネート、フェニレンジイソシアネート、４,４'-ジフェニルメタンジイソシアネート、４,４'-ジフェニルエーテルジイソシアネート、４,４'-ジフェニルスルホンジイソシアネート、キシリレンジイソシアネート、およびトリジンジイソシアネートが挙げられる。脂肪族ジイソシアネートとしては、例えば、エチレンジイソシアネート、プロピレンジイソシアネート、およびヘキサメチレンジイソシアネートが挙げられる。脂環式ジイソシアネートとしては、例えば、１,４-シクロヘキサンジイソシアネート、１,３-シクロヘキサンジイソシアネート、イソホロンジイソシアネート、および４,４'-ジシクロヘキシルメタンジイソシアネートが挙げられる。 Examples of the isocyanate component used in the above isocyanate method include aromatic diisocyanate, aliphatic diisocyanate, and alicyclic diisocyanate. Examples of aromatic diisocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyl ether diisocyanate, and 4,4′-diphenyl sulfone. Examples include diisocyanates, xylylene diisocyanates, and tolidine diisocyanates. Examples of the aliphatic diisocyanate include ethylene diisocyanate, propylene diisocyanate, and hexamethylene diisocyanate. Examples of the alicyclic diisocyanate include 1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate, isophorone diisocyanate, and 4,4′-dicyclohexylmethane diisocyanate.
　上記の酸クロライド法において用いられる酸クロライド成分としては、イソシアネート法に関して上記した酸成分における部分構造としてのカルボン酸の部位がカルボン酸クロライドに替わった構造を有するものが挙げられる。また、上記の酸クロライド法において用いられるアミン成分としては、イソシアネート法に関して上記したイソシアネート成分における部分構造としてのイソシアネートの部位がアミンに替わった構造を有するものが挙げられる。 Examples of the acid chloride component used in the acid chloride method include those having a structure in which the carboxylic acid moiety as a partial structure in the acid component described above with respect to the isocyanate method is replaced by carboxylic acid chloride. Moreover, as an amine component used in said acid chloride method, what has the structure which the site | part of the isocyanate as a partial structure in an isocyanate component mentioned above regarding the isocyanate method replaced with the amine is mentioned.
　ポリアミドイミド樹脂の合成に際して用いることのできる溶媒としては、例えば、Ｎ-メチル-２-ピロリドン、Ｎ,Ｎ-ジメチルホルムアミド、Ｎ,Ｎ-ジメチルアセトアミド、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、シクロヘキサノン、メチルエチルケトン、γ-ブチロラクトン、キシレン、およびトルエンが挙げられる。 Solvents that can be used in the synthesis of the polyamideimide resin include, for example, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, cyclohexanone, methyl ethyl ketone, γ -Butyrolactone, xylene, and toluene.
　樹脂組成物１０におけるＰＡＩ樹脂１１の含有量は、例えば８０～９９.９９質量％であり、好ましくは９０～９９.９９質量％、より好ましくは９２～９９.９９質量％、より好ましくは９４～９９.９９質量％、より好ましくは９５～９９.９９質量％である。 The content of the PAI resin 11 in the resin composition 10 is, for example, 80 to 99.99% by mass, preferably 90 to 99.99% by mass, more preferably 92 to 99.99% by mass, and more preferably 94 to It is 99.99% by mass, and more preferably 95 to 99.99% by mass.
　樹脂組成物１０に含有されるＮＤ粒子１２は、樹脂組成物１０中で熱安定剤ないし熱分解抑制剤としての機能を発揮するための成分であり、それぞれ、ナノダイヤモンド一次粒子またはナノダイヤモンド二次粒子である。ナノダイヤモンド一次粒子とは、粒径１０ｎｍ以下のナノダイヤモンドをいうものとする。また、樹脂組成物１０中のＮＤ粒子１２の粒径Ｄ５０（メディアン径）は、ＮＤ粒子１２について単位質量あたりの表面積を充分に確保して熱分解抑制剤としての機能を効率よく発揮させるという観点からは、好ましくは５００ｎｍ以下、より好ましくは３００ｎｍ以下、より好ましくは１００ｎｍ以下、より好ましくは８０ｎｍ以下である。ＮＤ粒子１２の粒径Ｄ５０は、例えば動的光散乱法によって測定することが可能である。 The ND particles 12 contained in the resin composition 10 are components for exhibiting a function as a heat stabilizer or a thermal decomposition inhibitor in the resin composition 10, and are respectively nanodiamond primary particles or nanodiamond secondary particles. Particles. The nanodiamond primary particles are nanodiamonds having a particle diameter of 10 nm or less. Further, the particle diameter D50 (median diameter) of the ND particles 12 in the resin composition 10 is a viewpoint that the surface area per unit mass of the ND particles 12 is sufficiently ensured and the function as a thermal decomposition inhibitor is efficiently exhibited. Is preferably 500 nm or less, more preferably 300 nm or less, more preferably 100 nm or less, and more preferably 80 nm or less. The particle size D50 of the ND particle 12 can be measured by, for example, a dynamic light scattering method.
　樹脂組成物１０に含有されるＮＤ粒子１２は、例えば爆轟法ナノダイヤモンド粒子（爆轟法によって生成したナノダイヤモンド粒子）である。爆轟法ナノダイヤモンド粒子については、例えば、次のようにして得ることができる。 The ND particles 12 contained in the resin composition 10 are, for example, detonation nanodiamond particles (nanodiamond particles generated by detonation). The detonation nanodiamond particles can be obtained, for example, as follows.
　まず、爆薬を密閉容器中で爆発させる。その際、使用爆薬が部分的に不完全燃焼を起こして遊離した炭素を原料として、爆発で生じた衝撃波の圧力とエネルギーの作用によってナノダイヤモンドが生成する。爆薬としては、トリニトロトルエン（ＴＮＴ）とシクロトリメチレントリニトロアミンすなわちヘキソーゲン（ＲＤＸ）との混合物を使用することができる。爆轟法で得られるナノダイヤモンド粗生成物には、金属酸化物が含まれやすい。この金属酸化物は、爆轟法に使用される容器等に由来するＦｅ，Ｃｏ，Ｎｉ等の酸化物である。例えば水溶媒中で所定の強酸を作用させることにより、ナノダイヤモンド粗生成物から金属酸化物を溶解・除去することができる（酸処理）。この酸処理に用いられる強酸としては、鉱酸が好ましく、例えば、塩酸、フッ化水素酸、硫酸、硝酸、および王水が挙げられる。また、爆轟法で得られるナノダイヤモンド粗生成物には、グラファイト（黒鉛）が含まれている。このグラファイトは、使用爆薬が部分的に不完全燃焼を起こして遊離した炭素のうちナノダイヤモンド結晶を形成しなかった炭素に由来する。例えば上記の酸処理を経た後に、例えば水溶媒中で所定の酸化剤を作用させることにより、ナノダイヤモンド粗生成物からグラファイトを除去することができる（酸化処理）。この酸化処理に用いられる酸化剤としては、例えば、クロム酸、無水クロム酸、二クロム酸、過マンガン酸、過塩素酸、及びこれらの塩、並びに、過酸化水素が挙げられる。爆轟法ナノダイヤモンド（爆轟法によって生成したナノダイヤモンド）は、以上のような酸処理および酸化処理を経て精製された後であっても、一次粒子間が非常に強く相互作用して集成している凝着体（二次粒子）の形態をとる。この凝着体を所定の分散媒に分散させて得られる懸濁液を解砕処理に付すことによって、粒径が一桁ナノメートルのナノダイヤモンドを得ることができる。分散媒としては、ナノダイヤモンドが溶解性を示し得る溶媒が好ましく、例えば、水、メタノール、エタノール、エチレングリコール、およびＮ-メチル-２-ピロリドンが挙げられる。解砕処理は、例えば、高剪断ミキサー、ハイシアーミキサー、ホモミキサー、ボールミル、ビーズミル、高圧ホモジナイザー、超音波ホモジナイザー、またはコロイドミルを使用して行うことができる。また、上記のような解砕処理の後、ナノダイヤモンドの分散している懸濁液の水分量を必要に応じて低減することによって、所定濃度のナノダイヤモンド分散液を得ることができる。或いは、上記のような解砕処理の後、ナノダイヤモンドの分散している懸濁液から必要に応じて水分を除去することによって、ナノダイヤモンドの粉体を得ることができる。これら水分量低減や水分除去は、例えばエバポレーターや噴霧乾燥装置を使用して行うことができる。 First, explode explosives in a sealed container. At that time, nano-diamonds are generated by the action of the pressure and energy of the shock wave generated by the explosion, using carbon that is liberated due to partial incomplete combustion of the explosive used. As the explosive, a mixture of trinitrotoluene (TNT) and cyclotrimethylenetrinitroamine, ie hexogen (RDX), can be used. The nanodiamond crude product obtained by the detonation method is likely to contain a metal oxide. This metal oxide is an oxide such as Fe, Co, or Ni derived from a container or the like used in the detonation method. For example, by applying a predetermined strong acid in an aqueous solvent, the metal oxide can be dissolved and removed from the nanodiamond crude product (acid treatment). The strong acid used for this acid treatment is preferably a mineral acid, and examples thereof include hydrochloric acid, hydrofluoric acid, sulfuric acid, nitric acid, and aqua regia. In addition, the nano-diamond crude product obtained by the detonation method contains graphite. This graphite is derived from carbon that did not form nanodiamond crystals among the carbon released by partial incomplete combustion of the explosive used. For example, after the above acid treatment, graphite can be removed from the nanodiamond crude product (oxidation treatment) by applying a predetermined oxidizing agent in an aqueous solvent, for example. Examples of the oxidizing agent used in the oxidation treatment include chromic acid, chromic anhydride, dichromic acid, permanganic acid, perchloric acid, and salts thereof, and hydrogen peroxide. Detonation nanodiamonds (nanodiamonds produced by detonation method) are aggregated by a very strong interaction between primary particles even after purification through acid treatment and oxidation treatment as described above. It takes the form of adhering bodies (secondary particles). By subjecting the suspension obtained by dispersing this agglomerated material in a predetermined dispersion medium to a pulverization treatment, nanodiamonds having a particle size of single-digit nanometers can be obtained. As the dispersion medium, a solvent in which nanodiamond can exhibit solubility is preferable, and examples thereof include water, methanol, ethanol, ethylene glycol, and N-methyl-2-pyrrolidone. The crushing treatment can be performed using, for example, a high shear mixer, a high shear mixer, a homomixer, a ball mill, a bead mill, a high-pressure homogenizer, an ultrasonic homogenizer, or a colloid mill. In addition, after the crushing treatment as described above, a nanodiamond dispersion liquid having a predetermined concentration can be obtained by reducing the water content of the suspension in which nanodiamonds are dispersed, as necessary. Alternatively, after the crushing treatment as described above, the nanodiamond powder can be obtained by removing moisture from the suspension in which the nanodiamond is dispersed, if necessary. These water content reduction and water removal can be performed using, for example, an evaporator or a spray dryer.
　このようにして得られるナノダイヤモンド粒子ないしＮＤ粒子１２の１０％熱分解温度は、好ましくは４００℃以上、より好ましくは４２０℃以上、より好ましくは４５０℃以上、より好ましくは５００℃以上、より好ましくは５２０℃以上である。このような構成は、樹脂組成物１０において高い耐熱性を実現するのに資する。本実施形態において、１０％熱分解温度とは、測定対象について空気雰囲気下で２０℃/分の昇温速度で昇温しながら重量減少を測定する場合に初期重量（基準重量）からの重量減少率が１０％に至るときの温度であり、例えば、実施例に関して後記する手法で測定することができる。 The 10% pyrolysis temperature of the nanodiamond particles or ND particles 12 thus obtained is preferably 400 ° C. or higher, more preferably 420 ° C. or higher, more preferably 450 ° C. or higher, more preferably 500 ° C. or higher, more preferably Is 520 ° C. or higher. Such a configuration contributes to realizing high heat resistance in the resin composition 10. In the present embodiment, the 10% pyrolysis temperature is a weight reduction from the initial weight (reference weight) when measuring the weight loss while raising the temperature of the object to be measured at 20 ° C./min. This is the temperature at which the rate reaches 10%, and can be measured, for example, by the method described later with respect to the examples.
　ＮＤ粒子１２の含有量は、樹脂組成物１０中のＰＡＩ樹脂１１とＮＤ粒子１２との総量に対して好ましくは０.０１～２０質量％である。ＮＤ粒子１２の当該含有量が多いほど、ＮＤ粒子１２の存在に起因する熱分解抑制効果は大きい傾向にあるところ、ＮＤ粒子１２の当該含有量の下限は、より好ましくは０.１質量％、より好ましくは１質量％である。樹脂組成物１０においてＰＡＩ樹脂１１による樹脂特性を適切に発現させるという観点からは、ＮＤ粒子１２の当該含有量は２０質量％以下であるのが好ましい場合がある。また、樹脂組成物１０中のＮＤ粒子１２の存在に起因する効果をより少量のＮＤ粒子１２で享受するという観点からは、ＮＤ粒子１２の当該含有量の上限は、より好ましくは１０質量％、より好ましくは８質量％、より好ましくは６質量％である。 The content of the ND particles 12 is preferably 0.01 to 20% by mass with respect to the total amount of the PAI resin 11 and the ND particles 12 in the resin composition 10. As the content of the ND particles 12 increases, the thermal decomposition inhibiting effect due to the presence of the ND particles 12 tends to increase. However, the lower limit of the content of the ND particles 12 is more preferably 0.1% by mass, More preferably, it is 1 mass%. From the viewpoint of appropriately expressing the resin characteristics of the PAI resin 11 in the resin composition 10, the content of the ND particles 12 may be preferably 20% by mass or less. Moreover, from the viewpoint of enjoying the effect due to the presence of the ND particles 12 in the resin composition 10 with a smaller amount of the ND particles 12, the upper limit of the content of the ND particles 12 is more preferably 10% by mass, More preferably, it is 8 mass%, More preferably, it is 6 mass%.
　樹脂組成物１０は、ＰＡＩ樹脂１１およびＮＤ粒子１２に加えて他の成分を含有してもよい。そのような他の成分としては、例えば、難燃剤、ガラス繊維、炭素繊維、帯電防止剤、滑剤、および着色剤が挙げられる。 Resin composition 10 may contain other components in addition to PAI resin 11 and ND particles 12. Examples of such other components include flame retardants, glass fibers, carbon fibers, antistatic agents, lubricants, and colorants.
　樹脂組成物１０は、樹脂成分として、上述のようにポリアミドイミド樹脂（ＰＡＩ樹脂）１１を含む。ＰＡＩ樹脂１１は、アミド結合とイミド結合とを合わせもつところ、樹脂構造に組み込まれたアミド結合は樹脂に熱成形性ないし加工性をもたらし、且つ、樹脂構造に組み込まれたイミド結合は樹脂に耐熱性をもたらす。このようなＰＡＩ樹脂１１を樹脂成分として含む樹脂組成物１０は、熱可塑性樹脂材料として高い耐熱性を実現するのに適する。また、ＰＡＩ樹脂１１においてイミド結合は樹脂に耐熱性に加えて機械的強度をももたらし且つアミド結合は樹脂に加工性に加えて強靭性をももたらすところ、このようなＰＡＩ樹脂１１を樹脂成分として含む樹脂組成物１０は、スーパーエンジニアリングプラスチックと呼称される高機能熱可塑性樹脂材料として用いることも可能である。 Resin composition 10 includes polyamideimide resin (PAI resin) 11 as a resin component as described above. The PAI resin 11 has both an amide bond and an imide bond. The amide bond incorporated in the resin structure brings thermoformability or processability to the resin, and the imide bond incorporated in the resin structure is heat resistant to the resin. Bring sex. The resin composition 10 containing such a PAI resin 11 as a resin component is suitable for realizing high heat resistance as a thermoplastic resin material. In the PAI resin 11, the imide bond brings mechanical strength to the resin in addition to heat resistance, and the amide bond brings toughness to the resin in addition to processability. Such PAI resin 11 is used as a resin component. The resin composition 10 to be included can also be used as a high-functional thermoplastic resin material called a super engineering plastic.
　加えて、樹脂組成物１０は、上述のようなナノダイヤモンド粒子（ＮＤ粒子）１２を含む。上述のように耐熱性の高いＰＡＩ樹脂１１の耐熱性を更に向上させる効果がＮＤ粒子１２にあること、具体的には、後記の実施例および比較例をもって示すようにＰＡＩ樹脂１１の熱分解を抑制する効果がＮＤ粒子１２にあることを、本発明者らは見出した。ＮＤ粒子１２は例えば４００℃を超える高温環境下でも耐熱性を示し得るものであるところ、そのようなＮＤ粒子１２をなすか或いはこれに含まれるナノダイヤモンド一次粒子の表面の少なくとも一部、即ち少なくとも｛１１１｝面には、ダイヤモンド本体をなすｓｐ3構造炭素からの自発転移によってｓｐ2構造炭素が生じているものと想定される。ナノダイヤモンド表面におけるこのｓｐ2構造炭素の存在が、高温環境下の樹脂材料中に発生するラジカルの補足や安定化に寄与し得て、従って、ラジカルの作用によるＰＡＩ樹脂１１の熱分解が抑制されるものと考えられる。 In addition, the resin composition 10 includes nanodiamond particles (ND particles) 12 as described above. As described above, the ND particles 12 have the effect of further improving the heat resistance of the PAI resin 11 having high heat resistance. Specifically, as shown in the examples and comparative examples described later, the PAI resin 11 is thermally decomposed. The present inventors have found that the ND particles 12 have an inhibitory effect. The ND particles 12 can exhibit heat resistance even in a high temperature environment exceeding 400 ° C., for example. However, the ND particles 12 form at least a part of the surface of the nanodiamond primary particles that form the ND particles 12 or are included in the ND particles 12, that is, at least It is assumed that sp 2 structure carbon is generated on the {111} plane by spontaneous transition from the sp 3 structure carbon forming the diamond body. The presence of this sp 2 structure carbon on the surface of the nanodiamond can contribute to the capture and stabilization of radicals generated in the resin material in a high temperature environment, and therefore, thermal decomposition of the PAI resin 11 due to the action of radicals is suppressed. It is thought that.
　以上のように、本実施形態の樹脂組成物１０は、高い耐熱性を実現するのに適するのである。樹脂組成物１０は、例えば、自動車等のエンジン用軸受の摺動材料を形成するための樹脂材料として使用することができる。また、樹脂組成物１０の表面抵抗率は、好ましくは１×１０12Ω/□以上、より好ましくは５×１０12Ω/□以上、より好ましくは１×１０13Ω/□以上である。このような構成によると、樹脂組成物１０について、高い耐熱性に加えて高い絶縁性を有する材料として用いることが可能となる。例えば、爆轟法によって生成した後に充分に精製されてグラファイト不純物の除去されたナノダイヤモンド粒子を樹脂組成物１０中のＮＤ粒子１２として用いることによって、樹脂組成物１０について低い表面抵抗率を実現することが可能である。 As described above, the resin composition 10 of the present embodiment is suitable for realizing high heat resistance. The resin composition 10 can be used, for example, as a resin material for forming a sliding material for an engine bearing such as an automobile. The surface resistivity of the resin composition 10 is preferably 1 × 10 12 Ω / □ or more, more preferably 5 × 10 12 Ω / □ or more, and more preferably 1 × 10 13 Ω / □ or more. According to such a configuration, the resin composition 10 can be used as a material having high insulation in addition to high heat resistance. For example, by using nano-diamond particles, which are produced by the detonation method and sufficiently purified to remove graphite impurities, as the ND particles 12 in the resin composition 10, a low surface resistivity is realized for the resin composition 10. It is possible.
　樹脂組成物１０については、例えば、上述のＰＡＩ樹脂１１と、上述のＮＤ粒子１２と、溶媒とを含有する硬化性組成物を基材に塗布した後に乾燥させることによって、作製することが可能である。この硬化性組成物の含有する溶媒としては、本実施形態では、ＰＡＩ樹脂１１が溶解性を示し且つＮＤ粒子１２が溶解性を示す例えば極性有機溶媒が用いられる。そのような極性有機溶媒としては、例えば、メタノール、エタノール、イソプロパノール、イソブチルアルコール、エチレングリコール、プロピレングリコール、グリセリン、２-メトキシエタノール、ジメチルスルホキシド、Ｎ-メチル-２-ピロリドン、アセトニトリル、Ｎ,Ｎ-ジメチルホルムアミド、Ｎ,Ｎ-ジメチルアセトアミド、Ｎ,Ｎ-ジエチルホルムアミド、Ｎ,Ｎ-ジエチルアセトアミド、Ｎ,Ｎ-ジメチルメトキシアセトアミド、ヘキサメチルホスホルアミド、ジメチルスルホン、γ-ブチロラクトン、α-アセチル-γ-ブチロラクトン、１,３-ジメチル-３,４,５,６-テトラヒドロ-２(１Ｈ)-ピリミジノン、１,３-ジメチル-２-イミダゾリジノン、テトラメチル尿素、シクロヘキサノン、酢酸テトラヒドロフルフリル、および炭酸プロピレンが挙げられる。当該溶媒としては、一種類の溶媒が用いられてもよいし、二種類以上の溶媒が用いられてもよい。ＰＡＩ樹脂１１およびＮＤ粒子１２の溶解性がともに比較的に高いという観点からは、当該溶媒としては、Ｎ-メチル-２-ピロリドンが好ましい。また、上記の硬化性組成物の作製は、例えば、ＰＡＩ樹脂１１を含有する溶液とＮＤ粒子１２を含有する溶液との混合によって行うことができる。ＰＡＩ樹脂１１を含有する溶液としては、例えば、上述のイソシアネート法または酸クロライド法による合成が行われてＰＡＩ樹脂１１を含有する有機溶媒溶液、または、当該溶液について溶媒置換によって溶媒成分の置換操作を経た有機溶媒溶液を、用いることができる。ＮＤ粒子１２を含有する溶液としては、例えば、ＮＤ粒子１２の分散する水分散液について水から有機溶媒への溶媒置換操作を経た有機溶媒溶液を用いることができる。 The resin composition 10 can be produced, for example, by applying a curable composition containing the above-described PAI resin 11, the above-described ND particles 12, and a solvent to a substrate and then drying the substrate. is there. As the solvent contained in the curable composition, for example, a polar organic solvent in which the PAI resin 11 exhibits solubility and the ND particles 12 exhibit solubility is used in the present embodiment. Examples of such polar organic solvents include methanol, ethanol, isopropanol, isobutyl alcohol, ethylene glycol, propylene glycol, glycerin, 2-methoxyethanol, dimethyl sulfoxide, N-methyl-2-pyrrolidone, acetonitrile, N, N- Dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, hexamethylphosphoramide, dimethylsulfone, γ-butyrolactone, α-acetyl-γ -Butyrolactone, 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone, 1,3-dimethyl-2-imidazolidinone, tetramethylurea, cyclohexanone, tetrahydrofurfuryl acetate, and And propylene carbonate That. As the solvent, one type of solvent may be used, or two or more types of solvents may be used. From the viewpoint that both the PAI resin 11 and the ND particles 12 have relatively high solubility, N-methyl-2-pyrrolidone is preferable as the solvent. Moreover, preparation of said curable composition can be performed by mixing the solution containing PAI resin 11 and the solution containing ND particle | grains 12, for example. As the solution containing the PAI resin 11, for example, an organic solvent solution containing the PAI resin 11 synthesized by the above-described isocyanate method or acid chloride method, or a solvent component replacement operation by solvent replacement of the solution is used. The passed organic solvent solution can be used. As the solution containing the ND particles 12, for example, an organic solvent solution obtained by subjecting the aqueous dispersion in which the ND particles 12 are dispersed to a solvent replacement operation from water to an organic solvent can be used.
　ＰＡＩ樹脂１１と、ＮＤ粒子１２と、溶媒とを含有する上述の硬化性組成物において、ＰＡＩ樹脂１１の含有量は例えば５～２０質量％であり、ＮＤ粒子１２の含有量は、ＰＡＩ樹脂１１とＮＤ粒子１２の総量に対して好ましくは０.０１～２０質量％である。ＮＤ粒子１２の当該含有量が多いほど、形成される樹脂組成物１０において、ＮＤ粒子１２の存在に起因する熱分解抑制効果は大きい傾向にあるところ、ＮＤ粒子１２の当該含有量の下限は、より好ましくは０.１質量％、より好ましくは１質量％である。形成される樹脂組成物１０においてＰＡＩ樹脂１１による樹脂特性を適切に発現させるという観点からは、ＮＤ粒子１２の当該含有量は２０質量％以下であるのが好ましい場合がある。また、形成される樹脂組成物１０中のＮＤ粒子１２の存在に起因する効果をより少量のＮＤ粒子１２で享受するという観点からは、ＮＤ粒子１２の当該含有量の上限は、より好ましくは１０質量％、より好ましくは８質量％、より好ましくは６質量％である。 In the curable composition containing the PAI resin 11, the ND particles 12 and the solvent, the content of the PAI resin 11 is, for example, 5 to 20% by mass, and the content of the ND particles 12 is The total amount of ND particles 12 is preferably 0.01 to 20% by mass. As the content of the ND particles 12 increases, the thermal decomposition inhibiting effect due to the presence of the ND particles 12 tends to increase in the resin composition 10 to be formed, and the lower limit of the content of the ND particles 12 is, More preferably, it is 0.1 mass%, More preferably, it is 1 mass%. From the viewpoint of appropriately developing the resin characteristics of the PAI resin 11 in the resin composition 10 to be formed, the content of the ND particles 12 may be preferably 20% by mass or less. Further, from the viewpoint of enjoying the effect due to the presence of the ND particles 12 in the resin composition 10 to be formed with a smaller amount of the ND particles 12, the upper limit of the content of the ND particles 12 is more preferably 10 It is 8 mass%, More preferably, it is 8 mass%, More preferably, it is 6 mass%.
［実施例１］
〔硬化性組成物の作製〕
　次のような溶媒置換工程および混合工程を経て、硬化性組成物を作製した。 [Example 1]
(Preparation of curable composition)
The curable composition was produced through the following solvent substitution steps and mixing steps.
　溶媒置換工程では、ナノダイヤモンド水分散液（商品名「Ｖｏｘ Ｄ」，固形分濃度ないしナノダイヤモンド濃度は５質量％，水溶媒，粒径Ｄ５０は５ｎｍ,ｐＨ９におけるゼータ電位は－５５ｍＶ，Ｃａｒｂｏｄｅｏｎ社製）の溶媒たる水をＮ-メチル-２-ピロリドン（ＮＭＰ，沸点２０２℃）に置換した。具体的には、当該ナノダイヤモンド水分散液２.３ｇにＮＭＰ（濃度９９.５質量％，キシダ化学株式会社製）６０ｇを加えて混合し、エバポレーターを使用して、当該混合物を加熱および減圧の条件下に置いた。エバポレーターによる溶媒置換操作では、当該混合物について、スターラーで撹拌しつつ、１.５ｋＰａの減圧条件下で初期温度４５℃から８０℃に２５分かけて昇温させ、その後、１.５ｋＰａの減圧条件下で、約２０分間、８０℃を維持した。このような溶媒置換操作を経て、ナノダイヤモンド粒子のＮＭＰ分散液を作製した。このナノダイヤモンドＮＭＰ分散液のナノダイヤモンド固形分濃度は２.０質量％であった。本分散液に含まれるナノダイヤモンド粒子の粒径について、スペクトリス株式会社製の装置（商品名「ゼータサイザー ナノＺＳ」）を使用して動的光散乱法によって測定したところ、粒径Ｄ５０（メディアン径）は１２.４ｎｍであった。 In the solvent replacement step, a nanodiamond aqueous dispersion (trade name “Vox D”, solid content or nanodiamond concentration is 5 mass%, aqueous solvent, particle size D50 is 5 nm, zeta potential at pH 9 is −55 mV, manufactured by Carbodeon. ) Was replaced with N-methyl-2-pyrrolidone (NMP, boiling point 202 ° C.). Specifically, 60 g of NMP (concentration 99.5% by mass, manufactured by Kishida Chemical Co., Ltd.) is added to 2.3 g of the nanodiamond aqueous dispersion and mixed, and the mixture is heated and decompressed using an evaporator. Placed under conditions. In the solvent replacement operation using an evaporator, the mixture is heated with a stirrer under a reduced pressure of 1.5 kPa from an initial temperature of 45 ° C. to 80 ° C. over 25 minutes, and then under reduced pressure of 1.5 kPa. At 80 ° C. for about 20 minutes. Through such solvent replacement operation, an NMP dispersion of nanodiamond particles was prepared. The nanodiamond NMP dispersion had a nanodiamond solid content concentration of 2.0% by mass. The particle size of the nanodiamond particles contained in this dispersion was measured by a dynamic light scattering method using an apparatus (trade name “Zetasizer Nano ZS”) manufactured by Spectris Co., Ltd. ) Was 12.4 nm.
　次の混合工程では、上述のようにして作製されたナノダイヤモンドＮＭＰ分散液と、ポリアミドイミド樹脂含有溶液（商品名「バイロマックス ＨＲ－１１ＮＮ」，固形分濃度ないしポリアミドイミド樹脂濃度は１５質量％，ＮＭＰ溶媒，東洋紡株式会社製）とを混合した。具体的には、このポリアミドイミド樹脂含有溶液を撹拌しつつこれに上述のナノダイヤモンドＮＭＰ分散液を滴下操作によって添加し、ポリアミドイミド樹脂９５質量部に対するナノダイヤモンド含有量が５質量部となる量比で、ポリアミドイミド樹脂含有溶液とナノダイヤモンドＮＭＰ分散液とを混合した。以上のようにして、ポリアミドイミド樹脂と、ナノダイヤモンド粒子と、溶媒たるＮＭＰとを含有する実施例１の硬化性組成物を作製した。 In the next mixing step, the nanodiamond NMP dispersion prepared as described above and a polyamideimide resin-containing solution (trade name “Bilomax® HR-11NN”, solid content concentration or polyamideimide resin concentration is 15% by mass, NMP solvent, manufactured by Toyobo Co., Ltd.). Specifically, while stirring the polyamideimide resin-containing solution, the above-mentioned nanodiamond NMP dispersion is added thereto by a dropping operation, so that the nanodiamond content with respect to 95 parts by mass of the polyamideimide resin is 5 parts by mass. Then, the polyamideimide resin-containing solution and the nanodiamond NMP dispersion were mixed. As described above, the curable composition of Example 1 containing polyamideimide resin, nanodiamond particles, and NMP as a solvent was produced.
〔熱可塑性樹脂組成物の作製〕
　以上のようにして作製された実施例１の硬化性組成物から、熱可塑性樹脂組成物を作製した。まず、スキージを使用して、ガラス板上に所定の厚さで硬化性組成物を塗布した。そして、硬化性組成物の塗膜の形成された当該ガラス板をマッフル炉内に入れて窒素雰囲気下で焼成処理した。具体的には、まず、１３０℃で１０分間の加熱を行い、次に、１３０℃から３００℃に６０分間かけて昇温し、その後、３００℃で６０分間の加熱を行った。以上のようにして、ポリアミドイミド樹脂およびナノダイヤモンド粒子を含有する実施例１の熱可塑性樹脂組成物、即ち、ポリアミドイミド樹脂とナノダイヤモンド粒子とが複合化された実施例１の樹脂フィルムを作製した。この樹脂フィルムについて、ナノダイヤモンド含有量は５質量％であり、厚さは２０μｍである。 [Preparation of thermoplastic resin composition]
A thermoplastic resin composition was produced from the curable composition of Example 1 produced as described above. First, using a squeegee, the curable composition was applied on a glass plate with a predetermined thickness. And the said glass plate in which the coating film of the curable composition was formed was put in the muffle furnace, and it baked in nitrogen atmosphere. Specifically, first, heating was performed at 130 ° C. for 10 minutes, then the temperature was increased from 130 ° C. to 300 ° C. over 60 minutes, and then heating was performed at 300 ° C. for 60 minutes. As described above, a thermoplastic resin composition of Example 1 containing a polyamideimide resin and nanodiamond particles, that is, a resin film of Example 1 in which a polyamideimide resin and nanodiamond particles were combined was prepared. . About this resin film, nanodiamond content is 5 mass% and thickness is 20 micrometers.
〔熱重量測定〕
　以上のようにして作製された実施例１の樹脂フィルムについて、熱重量測定装置(商品名「ＴＧ-ＤＴＡ６３００」，エスアイアイ・ナノテクノロジー株式会社製）を使用して、空気雰囲気下にて４６０℃で保持する間の重量減少量を測定した。本測定においては、４６０℃で１０分間保持された時点での測定対象の重量を基準重量（初期重量）とした。その結果を、図２のグラフにおいて線Ｅ１をもって表す。図２に示すグラフにおいて、横軸は、測定対象の４６０℃での保持時間たる時間（分）を表し、縦軸は、基準重量からの重量変化率としてのＴＧ（％）を表す。実施例１の樹脂フィルムが４６０℃で６０分間保持された時点、即ち、実施例１の樹脂フィルムが基準重量に至った時点から４６０℃で５０分間保持された時点での重量変化率は－１３.１％、即ち重量減少率は１３.１％、であった。 [Thermogravimetry]
About the resin film of Example 1 produced as described above, using a thermogravimetric measuring device (trade name “TG-DTA6300”, manufactured by SII Nano Technology Co., Ltd.), 460 ° C. in an air atmosphere. The weight loss during the holding was measured. In this measurement, the weight of the measurement object when held at 460 ° C. for 10 minutes was defined as the reference weight (initial weight). The result is represented by a line E1 in the graph of FIG. In the graph shown in FIG. 2, the horizontal axis represents the time (minutes) that is the retention time of the measurement target at 460 ° C., and the vertical axis represents TG (%) as the weight change rate from the reference weight. When the resin film of Example 1 was held at 460 ° C. for 60 minutes, that is, when the resin film of Example 1 reached the reference weight and was held at 460 ° C. for 50 minutes, the weight change rate was −13 0.1%, that is, the weight reduction rate was 13.1%.
　また、実施例１の樹脂フィルムについて、熱重量測定装置(商品名「ＴＧ-ＤＴＡ６３００」，エスアイアイ・ナノテクノロジー株式会社製）を使用して、空気雰囲気下にて４１０℃で保持する間の重量減少量を測定した。本測定においては、４１０℃で１０分間保持された時点での測定対象の重量を基準重量（初期重量）とした。その結果を、図３のグラフにおいて線Ｅ１をもって表す。図３に示すグラフにおいて、横軸は、測定対象の４１０℃での保持時間たる時間（分）を表し、縦軸は、基準重量からの重量変化率としてのＴＧ（％）を表す。実施例１の樹脂フィルムが４１０℃で６０分間保持された時点、即ち、実施例１の樹脂フィルムが基準重量に至った時点から４１０℃で５０分間保持された時点での重量変化率は－３.７６％、即ち重量減少率は３.７６％、であった。 Moreover, about the resin film of Example 1, the weight while hold | maintaining at 410 degreeC in an air atmosphere using a thermogravimetry apparatus (brand name "TG-DTA6300", SII nanotechnology Co., Ltd. make). The amount of decrease was measured. In this measurement, the weight of the measurement object when held at 410 ° C. for 10 minutes was defined as the reference weight (initial weight). The result is represented by a line E1 in the graph of FIG. In the graph shown in FIG. 3, the horizontal axis represents the time (minutes) that is the holding time of the measurement target at 410 ° C., and the vertical axis represents TG (%) as the weight change rate from the reference weight. When the resin film of Example 1 was held at 410 ° C. for 60 minutes, that is, when the resin film of Example 1 reached the reference weight and was held at 410 ° C. for 50 minutes, the weight change rate was −3 It was .76%, that is, the weight reduction rate was 3.76%.
〔表面抵抗率測定〕
　上述のようにして作製された実施例１の樹脂フィルムについて、抵抗率計(商品名「ハイレスタＵＰ ＭＣＰ-ＨＳＴ４５０」，株式会社三菱化学アナリテック製）を使用して、表面抵抗率を測定した。本測定は、２５℃および相対湿度５０％の環境下で行った。その結果、実施例１の樹脂フィルムは、測定限界である１×１０13Ω/□以上の表面抵抗率を示すことが判った。 (Surface resistivity measurement)
About the resin film of Example 1 produced as described above, the surface resistivity was measured using a resistivity meter (trade name “HIRESTA UP MCP-HST450”, manufactured by Mitsubishi Chemical Analytech Co., Ltd.). This measurement was performed in an environment of 25 ° C. and a relative humidity of 50%. As a result, it was found that the resin film of Example 1 exhibited a surface resistivity of 1 × 10 13 Ω / □ or more, which is a measurement limit.
［実施例２］
〔硬化性組成物の作製〕
　実施例１で用いたナノダイヤモンド水分散液の代わりに別途用意したナノダイヤモンド水分散液（固形分濃度ないしナノダイヤモンド濃度は１.０８質量％，水溶媒，粒径Ｄ５０は６.０４ｎｍ，ｐＨ６でのゼータ電位は－４２ｍＶ，株式会社ダイセル製）を用いた以外は実施例１の溶媒置換工程と同様にして、ナノダイヤモンド水分散液の溶媒たる水をＮＭＰに置換した（溶媒置換工程）。こうして得られたナノダイヤモンドＮＭＰ分散液のナノダイヤモンド固形分濃度は２.０質量％であった。本分散液に含まれるナノダイヤモンド粒子の粒径について、実施例１と同様にして動的光散乱法によって測定したところ、粒径Ｄ５０（メディアン径）は６.８３ｎｍであった。次の混合工程では、得られたナノダイヤモンドＮＭＰ分散液と、ポリアミドイミド樹脂含有溶液（商品名「バイロマックス ＨＲ-１１ＮＮ」，東洋紡株式会社製）とを混合した。具体的には、このポリアミドイミド樹脂含有溶液を撹拌しつつこれに上述のナノダイヤモンドＮＭＰ分散液を滴下操作によって添加し、ポリアミドイミド樹脂９５質量部に対するナノダイヤモンド含有量が５質量部となる量比で、ポリアミドイミド樹脂含有溶液とナノダイヤモンドＮＭＰ分散液とを混合した。以上のようにして、ポリアミドイミド樹脂と、ナノダイヤモンド粒子と、溶媒たるＮＭＰとを含有する実施例２の硬化性組成物を作製した。 [Example 2]
(Preparation of curable composition)
Nanodiamond aqueous dispersion prepared separately in place of the nanodiamond aqueous dispersion used in Example 1 (solid content concentration or nanodiamond concentration is 1.08% by mass, aqueous solvent, particle size D50 is 6.04 nm, pH 6) The water as the solvent of the nanodiamond aqueous dispersion was replaced with NMP (solvent replacement step) in the same manner as in the solvent replacement step of Example 1 except that the zeta potential of -42 mV, manufactured by Daicel Corporation) was used. The nanodiamond NMP dispersion thus obtained had a nanodiamond solid content concentration of 2.0% by mass. When the particle diameter of the nanodiamond particles contained in this dispersion was measured by the dynamic light scattering method in the same manner as in Example 1, the particle diameter D50 (median diameter) was 6.83 nm. In the next mixing step, the obtained nanodiamond NMP dispersion was mixed with a polyamideimide resin-containing solution (trade name “Vilomax HR-11NN”, manufactured by Toyobo Co., Ltd.). Specifically, while stirring the polyamideimide resin-containing solution, the above-mentioned nanodiamond NMP dispersion is added thereto by a dropping operation, so that the nanodiamond content with respect to 95 parts by mass of the polyamideimide resin is 5 parts by mass. Then, the polyamideimide resin-containing solution and the nanodiamond NMP dispersion were mixed. As described above, the curable composition of Example 2 containing polyamideimide resin, nanodiamond particles, and NMP as a solvent was produced.
〔熱可塑性樹脂組成物の作製〕
　実施例１の硬化性組成物に代えて実施例２の硬化性組成物を用いたこと以外は実施例１と同様にして、実施例２の熱可塑性樹脂組成物、即ち、ポリアミドイミド樹脂とナノダイヤモンド粒子とが複合化された実施例２の樹脂フィルムを作製した。この樹脂フィルムについて、ナノダイヤモンド含有量は５質量％であり、厚さは２０μｍである。 [Preparation of thermoplastic resin composition]
The thermoplastic resin composition of Example 2, i.e., the polyamideimide resin and the nanomaterial, was used in the same manner as in Example 1 except that the curable composition of Example 2 was used instead of the curable composition of Example 1. A resin film of Example 2 in which diamond particles were combined was produced. About this resin film, nanodiamond content is 5 mass% and thickness is 20 micrometers.
〔熱重量測定〕
　以上のようにして作製された実施例２の樹脂フィルムについて、実施例１の樹脂フィルムと同様に、熱重量測定装置(商品名「ＴＧ-ＤＴＡ６３００」）を使用して、空気雰囲気下にて４６０℃で保持する間の重量減少量を測定した。その結果を、図２のグラフにおいて線Ｅ２をもって表す。実施例２の樹脂フィルムが４６０℃で６０分間保持された時点、即ち、実施例２の樹脂フィルムが基準重量に至った時点から４６０℃で５０分間保持された時点での重量減少率は、２１.０％であった。 [Thermogravimetry]
About the resin film of Example 2 produced as described above, in the same manner as the resin film of Example 1, using a thermogravimetric measurement apparatus (trade name “TG-DTA6300”), 460 in an air atmosphere. The weight loss during holding at 0 ° C. was measured. The result is represented by a line E2 in the graph of FIG. When the resin film of Example 2 was held at 460 ° C. for 60 minutes, that is, when the resin film of Example 2 reached the reference weight and held at 460 ° C. for 50 minutes, the weight reduction rate was 21 0.0%.
〔表面抵抗率測定〕
　上述のようにして作製された実施例２の樹脂フィルムについて、実施例１の樹脂フィルムと同様にして、抵抗率計(商品名「ハイレスタＵＰ ＭＣＰ-ＨＳＴ４５０」，株式会社三菱化学アナリテック製）を使用して表面抵抗率を測定した。その結果、実施例２の樹脂フィルムは、測定限界である１×１０13Ω/□以上の表面抵抗率を示すことが判った。 (Surface resistivity measurement)
For the resin film of Example 2 produced as described above, a resistivity meter (trade name “HIRESTA UP MCP-HST450”, manufactured by Mitsubishi Chemical Analytech Co., Ltd.) was used in the same manner as the resin film of Example 1. Used to measure surface resistivity. As a result, it was found that the resin film of Example 2 exhibited a surface resistivity of 1 × 10 13 Ω / □ or more, which is a measurement limit.
［比較例１］
〔熱可塑性樹脂組成物の作製〕
　実施例１の硬化性組成物の代わりにポリアミドイミド樹脂含有溶液（商品名「バイロマックス ＨＲ-１１ＮＮ」，東洋紡株式会社製）を用いたこと以外は実施例１と同様にして、比較例１の熱可塑性樹脂組成物、即ち、比較例１のポリアミドイミド樹脂フィルムを作製した。この樹脂フィルムの厚さは２０μｍである。 [Comparative Example 1]
[Preparation of thermoplastic resin composition]
Comparative Example 1 is the same as Example 1 except that a polyamideimide resin-containing solution (trade name “Vilomax HR-11NN”, manufactured by Toyobo Co., Ltd.) is used instead of the curable composition of Example 1. A thermoplastic resin composition, that is, a polyamideimide resin film of Comparative Example 1 was produced. The resin film has a thickness of 20 μm.
〔熱重量測定〕
　比較例１のポリアミドイミド樹脂フィルムについて、実施例１の樹脂フィルムと同様に、熱重量測定装置(商品名「ＴＧ-ＤＴＡ６３００」）を使用して、空気雰囲気下にて４６０℃で保持する間の重量減少量を測定した。その結果を、図２のグラフにおいて線Ｃ１をもって表す。比較例１のポリアミドイミド樹脂フィルムが４６０℃で６０分間保持された時点、即ち、比較例１の樹脂フィルムが基準重量に至った時点から４６０℃で５０分間保持された時点での重量減少率は、２３.９％であった。 [Thermogravimetry]
About the polyamide-imide resin film of Comparative Example 1, in the same manner as the resin film of Example 1, using a thermogravimetric apparatus (trade name “TG-DTA6300”), while being held at 460 ° C. in an air atmosphere. The amount of weight loss was measured. The result is represented by a line C1 in the graph of FIG. When the polyamideimide resin film of Comparative Example 1 was held at 460 ° C. for 60 minutes, that is, when the resin film of Comparative Example 1 reached the reference weight and was held at 460 ° C. for 50 minutes, 23.9%.
　また、比較例１のポリアミドイミド樹脂フィルムについて、実施例１の樹脂フィルムと同様に、熱重量測定装置(商品名「ＴＧ-ＤＴＡ６３００」）を使用して、空気雰囲気下にて４１０℃で保持する間の重量減少量を測定した。その結果を、図３のグラフにおいて線Ｃ１をもって表す。比較例１のポリアミドイミド樹脂フィルムが４１０℃で６０分間保持された時点、即ち、比較例１の樹脂フィルムが基準重量に至った時点から４１０℃で５０分間保持された時点での重量減少率は、６.５８％であった。 Further, the polyamideimide resin film of Comparative Example 1 is held at 410 ° C. in an air atmosphere using a thermogravimetric measurement device (trade name “TG-DTA6300”) in the same manner as the resin film of Example 1. The amount of weight loss during was measured. The result is represented by a line C1 in the graph of FIG. When the polyamideimide resin film of Comparative Example 1 was held at 410 ° C. for 60 minutes, that is, when the resin film of Comparative Example 1 reached the reference weight and held at 410 ° C. for 50 minutes, 6.58%.
〔表面抵抗率測定〕
　上述のようにして作製された比較例１のポリアミドイミド樹脂フィルムについて、実施例１の樹脂フィルムと同様にして、抵抗率計(商品名「ハイレスタＵＰ ＭＣＰ-ＨＳＴ４５０」）を使用して表面抵抗率を測定した。その結果、比較例１の樹脂フィルムは、測定限界である１×１０13Ω/□以上の表面抵抗率を示した。 (Surface resistivity measurement)
About the polyamidoimide resin film of the comparative example 1 produced as mentioned above, it carries out similarly to the resin film of Example 1, and uses a resistivity meter (brand name "Hiresta UP MCP-HST450") and surface resistivity. Was measured. As a result, the resin film of Comparative Example 1 exhibited a surface resistivity of 1 × 10 13 Ω / □ or more, which is the measurement limit.
〈１０％熱分解温度測定〉
　実施例１,２のそれぞれにおいて使用したナノダイヤモンド水分散液に含まれているナノダイヤモンドについて、その１０％熱分解温度を測定した。具体的には、まず、サンドバスを使用して行う加熱乾燥によってナノダイヤモンド水分散液からナノダイヤモンド粉体を得た。次に、得られたナノダイヤモンド粉体について、熱重量測定装置（商品名「ＴＧ-ＤＴＡ６３００」，エスアイアイ・ナノテクノロジー株式会社製）を使用して、熱重量測定を行った。本測定では、測定対象について、その含有水分による測定結果への影響を充分に抑制すべく窒素雰囲気下にて２００℃で１０分間保持した後、空気雰囲気下で２００℃から８００℃まで昇温速度２０℃/分で昇温する過程での重量減少量を測定した。また、本測定では、２００℃で１０分間保持された時点での測定対象の重量を基準重量（初期重量）とした。その結果を、図４のグラフに示す。図４に示すグラフにおいて、横軸は温度（℃）を表し、縦軸は、基準重量（初期重量）からの重量変化率としてのＴＧ（％）を表す。図４のグラフでは、実施例１で使用したナノダイヤモンド粒子に係る測定結果について線Ｅ１'をもって表し、実施例２で使用したナノダイヤモンド粒子に係る測定結果について線Ｅ２'をもって表す。実施例１で使用したナノダイヤモンド粒子の１０％熱分解温度は５２５.４℃であった。実施例２で使用したナノダイヤモンド粒子の１０％熱分解温度は４２０.８℃であった。また、上述のポリアミドイミド樹脂含有溶液（商品名「バイロマックス ＨＲ-１１ＮＮ」）を塗布および乾燥して形成されるポリアミドイミド樹脂フィルムについて、熱重量測定装置（商品名「ＴＧ-ＤＴＡ６３００」，エスアイアイ・ナノテクノロジー株式会社製）を使用して、空気雰囲気下で３０℃から５５０℃まで昇温速度２０℃/分で昇温する過程での重量減少量を測定したところ、当該ポリアミドイミド樹脂の１０％熱分解温度は４９９℃であった。 <10% pyrolysis temperature measurement>
The nanodiamond contained in the nanodiamond aqueous dispersion used in each of Examples 1 and 2 was measured for its 10% thermal decomposition temperature. Specifically, first, nanodiamond powder was obtained from the nanodiamond aqueous dispersion by heat drying using a sand bath. Next, the obtained nanodiamond powder was subjected to thermogravimetric measurement using a thermogravimetric measurement device (trade name “TG-DTA6300”, manufactured by SII Nanotechnology Inc.). In this measurement, the measurement target is held at 200 ° C. for 10 minutes in a nitrogen atmosphere to sufficiently suppress the influence of the contained moisture on the measurement result, and then the rate of temperature increase from 200 ° C. to 800 ° C. in an air atmosphere The weight loss during the process of increasing the temperature at 20 ° C./min was measured. In this measurement, the weight of the object to be measured when it was held at 200 ° C. for 10 minutes was defined as the reference weight (initial weight). The result is shown in the graph of FIG. In the graph shown in FIG. 4, the horizontal axis represents temperature (° C.), and the vertical axis represents TG (%) as a weight change rate from the reference weight (initial weight). In the graph of FIG. 4, the measurement result relating to the nanodiamond particles used in Example 1 is represented by a line E1 ′, and the measurement result relating to the nanodiamond particles used in Example 2 is represented by a line E2 ′. The 10% pyrolysis temperature of the nanodiamond particles used in Example 1 was 525.4 ° C. The 10% pyrolysis temperature of the nanodiamond particles used in Example 2 was 40.8 ° C. In addition, for the polyamideimide resin film formed by applying and drying the above-mentioned solution containing polyamideimide resin (trade name “Vilomax HR-11NN”), a thermogravimetric measuring device (trade name “TG-DTA6300”, SII Using Nanotechnology Co., Ltd.), the amount of weight loss in the process of raising the temperature from 30 ° C. to 550 ° C. at a rate of temperature increase of 20 ° C./min under an air atmosphere was measured. The% thermal decomposition temperature was 499 ° C.
［評価］
　図２,３のグラフに示される結果から、ナノダイヤモンド粒子が内部に分散する実施例１,２の熱可塑性樹脂組成物たる樹脂フィルムは、ナノダイヤモンド粒子を含有しない比較例１のポリアミドイミド樹脂フィルムよりも、熱分解が抑制されていること、即ち耐熱性が高いことが、解る。また、図２のグラフに示される結果から、１０％熱分解温度が相対的に高いナノダイヤモンド粒子が内部に分散する実施例１の熱可塑性樹脂組成物たる樹脂フィルムは、１０％熱分解温度が相対的に低いナノダイヤモンド粒子が内部に分散する実施例２の熱可塑性樹脂組成物たる樹脂フィルムはよりも、熱分解が抑制されていることが、即ち耐熱性が高いことが、解る。 [Evaluation]
From the results shown in the graphs of FIGS. 2 and 3, the resin film as the thermoplastic resin composition of Examples 1 and 2 in which the nanodiamond particles are dispersed is the polyamideimide resin film of Comparative Example 1 that does not contain nanodiamond particles. It can be seen that thermal decomposition is suppressed, that is, heat resistance is high. Further, from the results shown in the graph of FIG. 2, the resin film which is the thermoplastic resin composition of Example 1 in which nanodiamond particles having a relatively high 10% pyrolysis temperature are dispersed therein has a 10% pyrolysis temperature. It can be seen that the thermal decomposition is suppressed, that is, the heat resistance is higher than that of the resin film which is the thermoplastic resin composition of Example 2 in which relatively low nano-diamond particles are dispersed.
　以上のまとめとして、本発明の構成およびそのバリエーションを以下に付記として列記する。 As a summary of the above, the configuration of the present invention and its variations are listed below as appendices.
〔付記１〕ポリアミドイミド樹脂と、ナノダイヤモンド粒子とを含む、熱可塑性樹脂組成物。
〔付記２〕前記ナノダイヤモンド粒子の１０％熱分解温度は４００℃以上である、付記１に記載の熱可塑性樹脂組成物。
〔付記３〕前記ナノダイヤモンド粒子の１０％熱分解温度は４２０℃以上である、付記１に記載の熱可塑性樹脂組成物。
〔付記４〕前記ナノダイヤモンド粒子の１０％熱分解温度は４５０℃以上である、付記１に記載の熱可塑性樹脂組成物。
〔付記５〕前記ナノダイヤモンド粒子の１０％熱分解温度は５００℃以上である、付記１に記載の熱可塑性樹脂組成物。
〔付記６〕前記ナノダイヤモンド粒子の１０％熱分解温度は５２０℃以上である、付記１に記載の熱可塑性樹脂組成物。
〔付記７〕前記ポリアミドイミド樹脂および前記ナノダイヤモンド粒子の合計含有量に対する前記ナノダイヤモンド粒子の含有量の割合が０.０１質量％以上である、付記１から６のいずれか一つに記載の熱可塑性樹脂組成物。
〔付記８〕前記ポリアミドイミド樹脂および前記ナノダイヤモンド粒子の合計含有量に対する前記ナノダイヤモンド粒子の含有量の割合が０.１質量％以上である、付記１から６のいずれか一つに記載の熱可塑性樹脂組成物。
〔付記９〕前記ポリアミドイミド樹脂および前記ナノダイヤモンド粒子の合計含有量に対する前記ナノダイヤモンド粒子の含有量の割合が１質量％以上である、付記１から６のいずれか一つに記載の熱可塑性樹脂組成物。
〔付記１０〕前記ポリアミドイミド樹脂および前記ナノダイヤモンド粒子の合計含有量に対する前記ナノダイヤモンド粒子の含有量の割合が２０質量％以下である、付記１から９のいずれか一つに記載の熱可塑性樹脂組成物。
〔付記１１〕前記ポリアミドイミド樹脂および前記ナノダイヤモンド粒子の合計含有量に対する前記ナノダイヤモンド粒子の含有量の割合が１０質量％以下である、付記１から９のいずれか一つに記載の熱可塑性樹脂組成物。
〔付記１２〕前記ポリアミドイミド樹脂および前記ナノダイヤモンド粒子の合計含有量に対する前記ナノダイヤモンド粒子の含有量の割合が８質量％以下である、付記１から９のいずれか一つに記載の熱可塑性樹脂組成物。
〔付記１３〕前記ポリアミドイミド樹脂および前記ナノダイヤモンド粒子の合計含有量に対する前記ナノダイヤモンド粒子の含有量の割合が６質量％以下である、付記１から９のいずれか一つに記載の熱可塑性樹脂組成物。
〔付記１４〕前記ナノダイヤモンド粒子は、爆轟法ナノダイヤモンド粒子である、付記１から１３のいずれか一つに記載の熱可塑性樹脂組成物。
〔付記１５〕前記ポリアミドイミド樹脂の含有量が８０質量％以上である、付記１から１４のいずれか一つに記載の熱可塑性樹脂組成物。
〔付記１６〕前記ポリアミドイミド樹脂の含有量が９０質量％以上である、付記１から１４のいずれか一つに記載の熱可塑性樹脂組成物。
〔付記１７〕前記ポリアミドイミド樹脂の含有量が９２質量％以上である、付記１から１４のいずれか一つに記載の熱可塑性樹脂組成物。
〔付記１８〕前記ポリアミドイミド樹脂の含有量が９４質量％以上である、付記１から１４のいずれか一つに記載の熱可塑性樹脂組成物。
〔付記１９〕前記ポリアミドイミド樹脂の含有量が９５質量％以上である、付記１から１４のいずれか一つに記載の熱可塑性樹脂組成物。
〔付記２０〕表面抵抗率が１×１０12Ω/□以上である、付記１から１９のいずれか一つに記載の熱可塑性樹脂組成物。
〔付記２１〕ポリアミドイミド樹脂と、ナノダイヤモンド粒子と、溶媒とを含む、硬化性組成物。
〔付記２２〕前記ナノダイヤモンド粒子の１０％熱分解温度は４００℃以上である、付記２１に記載の硬化性組成物。
〔付記２３〕前記ナノダイヤモンド粒子の１０％熱分解温度は４２０℃以上である、付記２１に記載の硬化性組成物。
〔付記２４〕前記ナノダイヤモンド粒子の１０％熱分解温度は４５０℃以上である、付記２１に記載の硬化性組成物。
〔付記２５〕前記ナノダイヤモンド粒子の１０％熱分解温度は５００℃以上である、付記２１に記載の硬化性組成物。
〔付記２６〕前記ナノダイヤモンド粒子の１０％熱分解温度は５２０℃以上である、付記２１に記載の硬化性組成物。
〔付記２７〕前記ポリアミドイミド樹脂および前記ナノダイヤモンド粒子の合計含有量に対する前記ナノダイヤモンド粒子の含有量の割合が０.０１質量％以上である、付記２２から２６のいずれか一つに記載の硬化性組成物。
〔付記２８〕前記ポリアミドイミド樹脂および前記ナノダイヤモンド粒子の合計含有量に対する前記ナノダイヤモンド粒子の含有量の割合が０.１質量％以上である、付記２２から２６のいずれか一つに記載の硬化性組成物。
〔付記２９〕前記ポリアミドイミド樹脂および前記ナノダイヤモンド粒子の合計含有量に対する前記ナノダイヤモンド粒子の含有量の割合が１質量％以上である、付記２２から２６のいずれか一つに記載の硬化性組成物。
〔付記３０〕前記ポリアミドイミド樹脂および前記ナノダイヤモンド粒子の合計含有量に対する前記ナノダイヤモンド粒子の含有量の割合が２０質量％以下である、付記２１から２９のいずれか一つに記載の硬化性組成物。
〔付記３１〕前記ポリアミドイミド樹脂および前記ナノダイヤモンド粒子の合計含有量に対する前記ナノダイヤモンド粒子の含有量の割合が１０質量％以下である、付記２１から２９のいずれか一つに記載の硬化性組成物。
〔付記３２〕前記ポリアミドイミド樹脂および前記ナノダイヤモンド粒子の合計含有量に対する前記ナノダイヤモンド粒子の含有量の割合が８質量％以下である、付記２１から２９のいずれか一つに記載の硬化性組成物。
〔付記３３〕前記ポリアミドイミド樹脂および前記ナノダイヤモンド粒子の合計含有量に対する前記ナノダイヤモンド粒子の含有量の割合が６質量％以下である、付記２１から２９のいずれか一つに記載の硬化性組成物。
〔付記３４〕前記ナノダイヤモンド粒子は、爆轟法ナノダイヤモンド粒子である、付記２１から３３のいずれか一つに記載の硬化性組成物。
〔付記３５〕前記溶媒は、極性有機溶媒である、付記２１から３４のいずれか一つに記載の硬化性組成物。
〔付記３６〕前記極性有機溶媒は、メタノール、エタノール、イソプロパノール、イソブチルアルコール、エチレングリコール、プロピレングリコール、グリセリン、２-メトキシエタノール、ジメチルスルホキシド、Ｎ-メチル-２-ピロリドン、アセトニトリル、Ｎ,Ｎ-ジメチルホルムアミド、Ｎ,Ｎ-ジメチルアセトアミド、Ｎ,Ｎ-ジエチルホルムアミド、Ｎ,Ｎ-ジエチルアセトアミド、Ｎ,Ｎ-ジメチルメトキシアセトアミド、ヘキサメチルホスホルアミド、ジメチルスルホン、γ-ブチロラクトン、α-アセチル-γ-ブチロラクトン、１,３-ジメチル-３,４,５,６-テトラヒドロ-２(１Ｈ)-ピリミジノン、１,３-ジメチル-２-イミダゾリジノン、テトラメチル尿素、シクロヘキサノン、酢酸テトラヒドロフルフリル、および炭酸プロピレンからなる群より選択される少なくとも一つを含む、付記３５に記載の硬化性組成物。 [Appendix 1] A thermoplastic resin composition comprising a polyamideimide resin and nanodiamond particles.
[Appendix 2] The thermoplastic resin composition according to Appendix 1, wherein the nanodiamond particles have a 10% thermal decomposition temperature of 400 ° C. or higher.
[Appendix 3] The thermoplastic resin composition according to Appendix 1, wherein the nanodiamond particles have a 10% thermal decomposition temperature of 420 ° C. or higher.
[Appendix 4] The thermoplastic resin composition according to Appendix 1, wherein the nanodiamond particles have a 10% thermal decomposition temperature of 450 ° C. or higher.
[Appendix 5] The thermoplastic resin composition according to Appendix 1, wherein the nanodiamond particles have a 10% thermal decomposition temperature of 500 ° C. or higher.
[Appendix 6] The thermoplastic resin composition according to Appendix 1, wherein the nanodiamond particles have a 10% thermal decomposition temperature of 520 ° C. or higher.
[Appendix 7] The heat according to any one of appendices 1 to 6, wherein a ratio of the content of the nanodiamond particles to the total content of the polyamideimide resin and the nanodiamond particles is 0.01% by mass or more. Plastic resin composition.
[Appendix 8] The heat according to any one of appendices 1 to 6, wherein a ratio of the content of the nanodiamond particles to the total content of the polyamideimide resin and the nanodiamond particles is 0.1% by mass or more. Plastic resin composition.
[Appendix 9] The thermoplastic resin according to any one of appendices 1 to 6, wherein a ratio of the content of the nanodiamond particles to the total content of the polyamideimide resin and the nanodiamond particles is 1% by mass or more. Composition.
[Appendix 10] The thermoplastic resin according to any one of appendices 1 to 9, wherein the ratio of the content of the nanodiamond particles to the total content of the polyamideimide resin and the nanodiamond particles is 20% by mass or less. Composition.
[Appendix 11] The thermoplastic resin according to any one of Appendixes 1 to 9, wherein a ratio of the content of the nanodiamond particles to a total content of the polyamideimide resin and the nanodiamond particles is 10% by mass or less. Composition.
[Appendix 12] The thermoplastic resin according to any one of Appendices 1 to 9, wherein the ratio of the content of the nanodiamond particles to the total content of the polyamideimide resin and the nanodiamond particles is 8% by mass or less. Composition.
[Appendix 13] The thermoplastic resin according to any one of appendices 1 to 9, wherein a ratio of the content of the nanodiamond particles to the total content of the polyamideimide resin and the nanodiamond particles is 6% by mass or less. Composition.
[Appendix 14] The thermoplastic resin composition according to any one of Appendixes 1 to 13, wherein the nanodiamond particles are detonation nanodiamond particles.
[Appendix 15] The thermoplastic resin composition according to any one of Appendixes 1 to 14, wherein the content of the polyamideimide resin is 80% by mass or more.
[Supplementary Note 16] The thermoplastic resin composition according to any one of Supplementary notes 1 to 14, wherein the content of the polyamideimide resin is 90% by mass or more.
[Appendix 17] The thermoplastic resin composition according to any one of Appendixes 1 to 14, wherein the content of the polyamideimide resin is 92% by mass or more.
[Appendix 18] The thermoplastic resin composition according to any one of Appendixes 1 to 14, wherein the content of the polyamideimide resin is 94% by mass or more.
[Appendix 19] The thermoplastic resin composition according to any one of appendices 1 to 14, wherein the content of the polyamideimide resin is 95% by mass or more.
[Appendix 20] The thermoplastic resin composition according to any one of Appendixes 1 to 19, wherein the surface resistivity is 1 × 10 12 Ω / □ or more.
[Appendix 21] A curable composition comprising a polyamideimide resin, nanodiamond particles, and a solvent.
[Appendix 22] The curable composition according to Appendix 21, wherein the nanodiamond particles have a 10% thermal decomposition temperature of 400 ° C. or higher.
[Appendix 23] The curable composition according to Appendix 21, wherein the nanodiamond particles have a 10% thermal decomposition temperature of 420 ° C. or higher.
[Appendix 24] The curable composition according to Appendix 21, wherein the nanodiamond particles have a 10% thermal decomposition temperature of 450 ° C. or higher.
[Appendix 25] The curable composition according to Appendix 21, wherein the nanodiamond particles have a 10% thermal decomposition temperature of 500 ° C. or higher.
[Appendix 26] The curable composition according to Appendix 21, wherein the nanodiamond particles have a 10% thermal decomposition temperature of 520 ° C. or higher.
[Supplementary note 27] The curing according to any one of Supplementary notes 22 to 26, wherein a ratio of the content of the nanodiamond particles to the total content of the polyamideimide resin and the nanodiamond particles is 0.01% by mass or more. Sex composition.
[Appendix 28] The curing according to any one of appendices 22 to 26, wherein the ratio of the content of the nanodiamond particles to the total content of the polyamideimide resin and the nanodiamond particles is 0.1% by mass or more. Sex composition.
[Supplementary note 29] The curable composition according to any one of Supplementary notes 22 to 26, wherein a ratio of the content of the nanodiamond particles to the total content of the polyamideimide resin and the nanodiamond particles is 1% by mass or more. object.
[Supplementary Note 30] The curable composition according to any one of Supplementary notes 21 to 29, wherein a ratio of the content of the nanodiamond particles to the total content of the polyamideimide resin and the nanodiamond particles is 20% by mass or less. object.
[Appendix 31] The curable composition according to any one of appendices 21 to 29, wherein a ratio of the content of the nanodiamond particles to the total content of the polyamideimide resin and the nanodiamond particles is 10% by mass or less. object.
[Supplementary Note 32] The curable composition according to any one of Supplementary Notes 21 to 29, wherein a ratio of the content of the nanodiamond particles to the total content of the polyamideimide resin and the nanodiamond particles is 8% by mass or less. object.
[Appendix 33] The curable composition according to any one of appendices 21 to 29, wherein the ratio of the content of the nanodiamond particles to the total content of the polyamideimide resin and the nanodiamond particles is 6% by mass or less. object.
[Appendix 34] The curable composition according to any one of appendices 21 to 33, wherein the nanodiamond particles are detonation nanodiamond particles.
[Appendix 35] The curable composition according to any one of Appendixes 21 to 34, wherein the solvent is a polar organic solvent.
[Appendix 36] The polar organic solvent is methanol, ethanol, isopropanol, isobutyl alcohol, ethylene glycol, propylene glycol, glycerin, 2-methoxyethanol, dimethyl sulfoxide, N-methyl-2-pyrrolidone, acetonitrile, N, N-dimethyl. Formamide, N, N-dimethylacetamide, N, N-diethylformamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, hexamethylphosphoramide, dimethylsulfone, γ-butyrolactone, α-acetyl-γ- Butyrolactone, 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone, 1,3-dimethyl-2-imidazolidinone, tetramethylurea, cyclohexanone, tetrahydrofurfuryl acetate, and carbonic acid Selected from the group consisting of propylene At least one containing curable composition according to Note 35 to be.
１０　樹脂組成物（熱可塑性樹脂組成物）
１１　ＰＡＩ樹脂（ポリアミドイミド樹脂）
１２　ＮＤ粒子（ナノダイヤモンド粒子） 10 Resin composition (thermoplastic resin composition)
11 PAI resin (polyamideimide resin)
12 ND particles (nanodiamond particles)

Claims (13)

  1. 　ポリアミドイミド樹脂と、ナノダイヤモンド粒子とを含む、熱可塑性樹脂組成物。 A thermoplastic resin composition comprising a polyamideimide resin and nanodiamond particles.
  2. 　前記ナノダイヤモンド粒子の１０％熱分解温度は４００℃以上である、請求項１に記載の熱可塑性樹脂組成物。 The thermoplastic resin composition according to claim 1, wherein the nanodiamond particles have a 10% thermal decomposition temperature of 400 ° C or higher.
  3. 　前記ポリアミドイミド樹脂および前記ナノダイヤモンド粒子の合計含有量に対する前記ナノダイヤモンド粒子の含有量の割合が０.０１質量％以上である、請求項１または２に記載の熱可塑性樹脂組成物。 The thermoplastic resin composition according to claim 1 or 2, wherein a ratio of the content of the nanodiamond particles to the total content of the polyamideimide resin and the nanodiamond particles is 0.01% by mass or more.
  4. 　前記ポリアミドイミド樹脂および前記ナノダイヤモンド粒子の合計含有量に対する前記ナノダイヤモンド粒子の含有量の割合が２０質量％以下である、請求項１から３のいずれか一つに記載の熱可塑性樹脂組成物。 The thermoplastic resin composition according to any one of claims 1 to 3, wherein a ratio of the content of the nanodiamond particles to the total content of the polyamideimide resin and the nanodiamond particles is 20% by mass or less.
  5. 　前記ナノダイヤモンド粒子は、爆轟法ナノダイヤモンド粒子である、請求項１から４のいずれか一つに記載の熱可塑性樹脂組成物。 The thermoplastic resin composition according to any one of claims 1 to 4, wherein the nanodiamond particles are detonation nanodiamond particles.
  6. 　表面抵抗率が１×１０12Ω/□以上である、請求項１から５のいずれか一つに記載の熱可塑性樹脂組成物。 The thermoplastic resin composition according to any one of claims 1 to 5, wherein the surface resistivity is 1 x 10 12 Ω / □ or more.
  7. 　ポリアミドイミド樹脂と、ナノダイヤモンド粒子と、溶媒とを含む、硬化性組成物。 A curable composition containing a polyamide-imide resin, nanodiamond particles, and a solvent.
  8. 　前記ナノダイヤモンド粒子の１０％熱分解温度は４００℃以上である、請求項７に記載の硬化性組成物。 The curable composition according to claim 7, wherein the nanodiamond particles have a 10% thermal decomposition temperature of 400 ° C. or higher.
  9. 　前記ポリアミドイミド樹脂および前記ナノダイヤモンド粒子の合計含有量に対する前記ナノダイヤモンド粒子の含有量の割合が０.０１質量％以上である、請求項７または８に記載の硬化性組成物。 The curable composition according to claim 7 or 8, wherein a ratio of the content of the nanodiamond particles to the total content of the polyamideimide resin and the nanodiamond particles is 0.01% by mass or more.
  10. 　前記ポリアミドイミド樹脂および前記ナノダイヤモンド粒子の合計含有量に対する前記ナノダイヤモンド粒子の含有量の割合が２０質量％以下である、請求項７から９のいずれか一つに記載の硬化性組成物。 The curable composition according to any one of claims 7 to 9, wherein a ratio of the content of the nanodiamond particles to the total content of the polyamideimide resin and the nanodiamond particles is 20% by mass or less.
  11. 　前記ナノダイヤモンド粒子は、爆轟法ナノダイヤモンド粒子である、請求項７から１０のいずれか一つに記載の硬化性組成物。 The curable composition according to any one of claims 7 to 10, wherein the nanodiamond particles are detonated nanodiamond particles.
  12. 　前記溶媒は、極性有機溶媒である、請求項７から１１のいずれか一つに記載の硬化性組成物。 The curable composition according to any one of claims 7 to 11, wherein the solvent is a polar organic solvent.
  13. 　前記極性有機溶媒は、メタノール、エタノール、イソプロパノール、イソブチルアルコール、エチレングリコール、プロピレングリコール、グリセリン、２-メトキシエタノール、ジメチルスルホキシド、Ｎ-メチル-２-ピロリドン、アセトニトリル、Ｎ,Ｎ-ジメチルホルムアミド、Ｎ,Ｎ-ジメチルアセトアミド、Ｎ,Ｎ-ジエチルホルムアミド、Ｎ,Ｎ-ジエチルアセトアミド、Ｎ,Ｎ-ジメチルメトキシアセトアミド、ヘキサメチルホスホルアミド、ジメチルスルホン、γ-ブチロラクトン、α-アセチル-γ-ブチロラクトン、１,３-ジメチル-３,４,５,６-テトラヒドロ-２(１Ｈ)-ピリミジノン、１,３-ジメチル-２-イミダゾリジノン、テトラメチル尿素、シクロヘキサノン、酢酸テトラヒドロフルフリル、および炭酸プロピレンからなる群より選択される少なくとも一つを含む、請求項１２に記載の硬化性組成物。 The polar organic solvent is methanol, ethanol, isopropanol, isobutyl alcohol, ethylene glycol, propylene glycol, glycerin, 2-methoxyethanol, dimethyl sulfoxide, N-methyl-2-pyrrolidone, acetonitrile, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, hexamethylphosphoramide, dimethylsulfone, γ-butyrolactone, α-acetyl-γ-butyrolactone, 1, The group consisting of 3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone, 1,3-dimethyl-2-imidazolidinone, tetramethylurea, cyclohexanone, tetrahydrofurfuryl acetate, and propylene carbonate Less selected Including one Kutomo, curable composition according to claim 12.
PCT/JP2017/006215 2016-05-19 2017-02-20 Thermoplastic resin composition and curable composition WO2017199499A1 (en)

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Publication number Priority date Publication date Assignee Title
WO2020026790A1 (en) * 2018-07-30 2020-02-06 株式会社ダイセル Surface-modified nanodiamond and dispersion and composite material containing surface-modified nanodiamond
JPWO2020026790A1 (en) * 2018-07-30 2021-08-02 株式会社ダイセル Surface-modified nanodiamonds, dispersions containing the surface-modified nanodiamonds, and composite materials
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