WO2017199499A1 - Composition de résine thermoplastique et composition durcissable - Google Patents

Composition de résine thermoplastique et composition durcissable Download PDF

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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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English (en)
Japanese (ja)
Inventor
久米篤史
梅本浩一
伊藤久義
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Daicel Corp
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Daicel Corp
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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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  • Chemical Kinetics & Catalysis (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)
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Abstract

Une composition de résine (10) comme la composition de résine thermoplastique de la présente invention comprend une résine de polyamide-imide (11) et des nanoparticules de diamant (12). La température de décomposition thermique à 10 % des nanoparticules de diamant (12) est, par exemple, de 400 °C ou plus. Une telle composition de résine thermoplastique permet d'obtenir une résistance élevée à la chaleur. Ladite composition durcissable comprend une résine de polyamide-imide (11), des nanoparticules de diamant (12), et un solvant. Une telle composition durcissable convient pour pouvoir obtenir une composition de résine thermoplastique permettant d'atteindre une résistance élevée à la chaleur.
PCT/JP2017/006215 2016-05-19 2017-02-20 Composition de résine thermoplastique et composition durcissable Ceased WO2017199499A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020026790A1 (fr) * 2018-07-30 2020-02-06 株式会社ダイセル Nanodiamant modifié en surface et dispersion et matériau composite contenant un nanodiamant modifié en surface

Citations (2)

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Publication number Priority date Publication date Assignee Title
JP2008101189A (ja) * 2006-09-19 2008-05-01 Nissan Motor Co Ltd 低摩擦摺動機構
JP2012201878A (ja) * 2011-03-28 2012-10-22 Vision Development Co Ltd ダイヤモンド含有複合樹脂組成物、及びその製造方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008101189A (ja) * 2006-09-19 2008-05-01 Nissan Motor Co Ltd 低摩擦摺動機構
JP2012201878A (ja) * 2011-03-28 2012-10-22 Vision Development Co Ltd ダイヤモンド含有複合樹脂組成物、及びその製造方法

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020026790A1 (fr) * 2018-07-30 2020-02-06 株式会社ダイセル Nanodiamant modifié en surface et dispersion et matériau composite contenant un nanodiamant modifié en surface
JPWO2020026790A1 (ja) * 2018-07-30 2021-08-02 株式会社ダイセル 表面修飾ナノダイヤモンド、前記表面修飾ナノダイヤモンドを含む分散液、及び複合材料
JP7404238B2 (ja) 2018-07-30 2023-12-25 株式会社ダイセル 表面修飾ナノダイヤモンドの製造方法、及び複合材料の製造方法

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