WO2018079597A1 - Additif destiné à des résines, et composition de résine - Google Patents

Additif destiné à des résines, et composition de résine Download PDF

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Publication number
WO2018079597A1
WO2018079597A1 PCT/JP2017/038500 JP2017038500W WO2018079597A1 WO 2018079597 A1 WO2018079597 A1 WO 2018079597A1 JP 2017038500 W JP2017038500 W JP 2017038500W WO 2018079597 A1 WO2018079597 A1 WO 2018079597A1
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resin
nanodiamond
additive
detonation
particles
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PCT/JP2017/038500
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English (en)
Japanese (ja)
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久米篤史
多田平八郎
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
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/02—Elements
    • C30B29/04—Diamond
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/25—Diamond
    • C01B32/26—Preparation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/25—Diamond
    • C01B32/28—After-treatment, e.g. purification, irradiation, separation or recovery

Definitions

  • the present invention relates to a resin additive used for, for example, a thermoplastic resin, and a resin composition containing the resin additive and a resin.
  • a resin having a function of trapping or stabilizing radicals may be added as an additive for a resin to a resin that undergoes a process involving heating for the purpose of preventing a decomposition reaction or a crosslinking reaction.
  • a resin additive a hindered phenol compound is generally used as described in Patent Documents 1 to 3 below.
  • resin materials having high heat resistance such as engineering plastics and super engineering plastics generally have a high melting point, and accordingly, a high processing temperature is required in the molding process.
  • a processing temperature as high as 280 ° C. or higher may be required.
  • additives for resins that are organic compounds such as the above-mentioned hindered phenol compounds
  • an object of the present invention is to provide a resin having a high heat resistance that can exhibit functions such as scavenging radicals even at a high processing temperature (for example, 280 ° C. or higher) while suppressing deterioration and thickening during heat processing of the resin.
  • a resin composition comprising the resin additive and a resin.
  • the metal content is 3000 ppm or less, and the maximum absorption peak at 1700 to 1850 cm ⁇ 1 is 2800 to 3000 cm in the infrared absorption spectrum by a Fourier transform infrared spectrophotometer (FT-IR).
  • FT-IR Fourier transform infrared spectrophotometer
  • the sodium content of the detonation nanodiamond particles is preferably 2000 ppm or less.
  • the resin additive of the present invention is preferably a heat stabilizer and / or an antioxidant.
  • the resin additive of the present invention is preferably one in which the detonation nanodiamond particles are pickled.
  • the resin additive of the present invention is preferably one obtained by vapor phase oxidation of the detonation nanodiamond particles.
  • the resin additive of the present invention preferably has a negative zeta potential of the detonation nanodiamond particles.
  • the additive for resin of the present invention has a maximum absorption peak of 1700 to 1850 cm ⁇ 1 in the infrared absorption spectrum of the detonation nanodiamond particles by Fourier transform infrared spectrophotometer (FT-IR). It is preferably present between 1740 and 1830 cm ⁇ 1 .
  • FT-IR Fourier transform infrared spectrophotometer
  • the present invention also provides a resin composition comprising the resin additive and a resin.
  • the resin is preferably a thermoplastic resin.
  • thermoplastic resin is preferably an aromatic polyether ketone.
  • the aromatic polyether ketone is at least one selected from the group consisting of polyether ketone, polyether ether ketone, polyether ketone ketone, and polyether ether ketone ketone. It is preferable.
  • the content of the resin additive is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the resin.
  • the additive for resin of the present invention has high heat resistance, can exhibit functions such as scavenging radicals even at a high processing temperature (for example, 280 ° C. or higher), and exhibits deterioration and thickening during heat processing of the resin. Can be suppressed.
  • ND1 nanodiamond
  • ND2 FT-IR spectrum of nanodiamond
  • ND3 FT-IR spectrum of nanodiamond
  • ND4 FT-IR spectrum of nanodiamond
  • ND5 FT-IR spectrum of nanodiamond
  • ND6 FT-IR spectrum of nanodiamond
  • the additive for resin of the present invention (hereinafter sometimes referred to as “the present invention”) has a metal content of 3000 ppm or less, and in the infrared absorption spectrum by a Fourier transform infrared spectrophotometer (FT-IR), maximum peak of the absorption peak of 1700 ⁇ 1850 cm -1 is characterized by using a detonation method nanodiamond particles being higher than the absorption peak of 2800 ⁇ 3000 cm -1.
  • FT-IR Fourier transform infrared spectrophotometer
  • the present invention is, for example, a thermal stabilizer, an antioxidant, an ultraviolet absorber, an ultraviolet stabilizer, a dispersion stabilizer, a flame retardant, a lubricant, and a (crystal) nucleating agent, preferably a thermal stabilizer, an antioxidant, more preferably Is a heat stabilizer.
  • the heat stabilizer is a compound having a function of capturing or stabilizing radicals.
  • detonation nanodiamond particles are nanodiamond particles obtained by the detonation method described later, and as detonation nanodiamonds, air-cooled detonation nanodiamond and water-cooled detonation are used. Any of the method nano diamonds may be used.
  • the detonation nanodiamond particles may be primary particles of nanodiamond or secondary particles of nanodiamond in which primary particles are assembled.
  • the nanodiamond primary particles particularly mean nanodiamond particles having a particle diameter of 10 nm or less.
  • the particle diameter D50 (median diameter) of the detonation nanodiamond particles is, for example, 10 ⁇ m or less, preferably 500 nm or less, more preferably 200 nm or less.
  • the particle size D50 is a particle size of primary particles of nanodiamond or secondary particles in which primary particles are assembled. When the particle size D50 of the detonation nanodiamond particles is 10 ⁇ m or less, a sufficient surface area per unit mass can be secured, and for example, functions as nanodiamonds such as a thermal stabilizer can be efficiently exhibited. .
  • Nano-diamond particles have a basic skeleton with a sp 3 structure of carbon atoms as in bulk diamond, but at least part of the surface of the nano-diamond primary particles is made of graphite by spontaneous transition from the sp 3 structure carbon forming the diamond body. It is assumed that a layer (graphite carbon layer) is generated. The presence of the sp 2 structure carbon in the graphite layer contributes to the capture and stabilization of radicals, and therefore, it is considered that the decomposition / crosslinking, that is, deterioration of the resin due to the action of radicals is suppressed.
  • the nanodiamond particles preferably have a hydroxyl group, a carboxyl group, a carbonyl group or the like as a group (surface functional group) bonded to the terminal carbon atom of the basic skeleton of nanodiamond.
  • These surface functional groups form a conjugated system in cooperation with the sp 2 structure carbon existing on the nanodiamond surface, contribute to the capture and stabilization of radicals, and suppress the decomposition and crosslinking of the resin due to the action of radicals, that is, deterioration. It is thought to work.
  • the ratio of hydroxyl-bonded carbon (C—OH) in the carbon contained in the detonation nanodiamond particles is, for example, 6.0% or more, preferably 7.0% or more, more preferably 8.0% or more, more preferably Is 10.0% or more, more preferably 12.0% or more.
  • the upper limit of the ratio of hydroxyl-bonded carbon is, for example, 40.0%.
  • the hydroxyl group-bonded carbon means carbon of the basic skeleton of nanodiamond, to which the surface functional group hydroxyl group (—OH) is bonded, in the basic skeleton of nanodiamond.
  • the ratio of the hydroxyl-bonded carbon can be measured, for example, by solid state 13 C-NMR analysis.
  • the upper limit of the ratio of carboxyl carbon is, for example, 5.0%.
  • the carboxyl carbon means carbon contained in a carboxyl group (—C ( ⁇ O) O including —COOH) which is a surface functional group.
  • the proportion of the carboxyl carbon can be measured, for example, by solid state 13 C-NMR analysis.
  • the proportion of carbonyl carbon (C ⁇ O) in the carbon contained in the detonation nanodiamond particles is, for example, 0.1% or more, preferably 0.2% or more, more preferably 0.3% or more, and more. Preferably it is 0.4% or more.
  • the upper limit of the carbonyl carbon ratio is, for example, 5.0%.
  • the carbonyl carbon means carbon contained in a carbonyl group (—C ⁇ O) which is a surface functional group. Note that carbon included in —C ( ⁇ O) O is not included in carbonyl carbon.
  • the proportion of the carbonyl carbon can be measured, for example, by solid state 13 C-NMR analysis.
  • the proportion of hydrogen-bonded carbon in the carbon contained in the detonation nanodiamond particles is, for example, 8.0% or more, preferably 9.0% or more, more preferably 10.0% or more, more preferably 12.0%. That's it.
  • the hydrogen-bonded carbon is a carbon that is bonded to a hydrogen atom present in the surface functional group. When the proportion of hydrogen-bonded carbon is 8.0% or more, it contributes to the stabilization of the surface carbon of the nanodiamond.
  • the proportion of the hydrogen-bonded carbon can be measured, for example, by solid state 13 C-NMR analysis.
  • the proportion of sp 3 carbon (carbon atom having sp 3 structure) in the carbon contained in the detonation nanodiamond particles is, for example, 50.0% or more, preferably 55.0% or more, more preferably 60.0%. As mentioned above, More preferably, it is 65.0% or more, More preferably, it is 70.0% or more. The upper limit of the proportion of sp 3 carbon is 90.0%.
  • the proportion of sp 3 carbon can be measured, for example, by solid state 13 C-NMR analysis.
  • the detonation nanodiamond particles are preferably pickled.
  • the acid used for the pickling treatment include hydrochloric acid, sulfuric acid, and nitric acid.
  • metal impurities in the nanodiamond particles can be effectively removed, and the metal content in the nanodiamond particles can be reduced.
  • the detonation nanodiamond particles may have been subjected to oxidation treatment such as solution oxidation treatment, oxygen oxidation (vapor phase oxidation) treatment in that the zeta potential of the nanodiamond particles can be negative. preferable.
  • the metal content in the detonation nanodiamond particles is 3000 ppm or less, for example, the total content (mass) of metal elements observed when detonation nanodiamond particles are analyzed by ICP emission spectroscopy. It means 3000 ppm or less.
  • the metal element include aluminum, chromium, copper, iron, sodium, titanium, calcium, potassium, silicon, and the like.
  • the metal content is 3000 ppm or less, preferably 2500 ppm or less, more preferably 2000 ppm or less, and more preferably 1500 ppm or less.
  • the metal impurities in the nanodiamond particles can be effectively removed, and the metal content in the nanodiamond particles can be reduced to 3000 ppm or less.
  • the metal content of the nanodiamond particles is 3000 ppm or less, for example, when a resin additive is used as a heat stabilizer, the function of trapping radicals can be exhibited more and the resin deteriorates during heat processing. And thickening can be suppressed.
  • the details of the ICP emission spectroscopic analysis are as described in the examples of the present application.
  • the metal content can be obtained by the method described in the examples of the present application.
  • content (mass) of sodium is 2000 ppm or less, for example, Preferably it is 1000 ppm or less, More preferably, it is 500 ppm or less, More preferably, it is 100 ppm or less.
  • content of sodium is large, sodium acts as a catalyst during heat processing of the resin and promotes thermal decomposition of the nanodiamond itself, which may reduce the heat resistance of the nanodiamond particles.
  • content of sodium is 2000 ppm or less, a decrease in heat resistance of the nanodiamond particles during heat processing can be suppressed.
  • the sodium content can also be determined by ICP emission spectroscopic analysis, for example, by the method described in the examples of the present application.
  • FT-IR Fourier transform infrared spectrophotometer
  • the maximum peak of the absorption peak means the maximum peak in a downward curve in which the transmittance is low in the case of a transmission spectrum in which the vertical axis is the transmittance (% TRANSMITTANCE) as shown in FIGS. Shall. Further, a high absorption peak means that the transmittance at the maximum peak is low.
  • the maximum peak of the absorption peak of 1700 to 1850 cm ⁇ 1 exists between 1740 and 1830 cm ⁇ 1 in the FT-IR infrared absorption spectrum of the detonation nanodiamond particles.
  • the surface functional group tends to have a higher ratio of C ⁇ O in the lactone or anhydride group than C ⁇ O in the ketone group, and in this case, the nanodiamond particles were considerably oxidized. It can be said that it is in a state.
  • the surface functional groups of the detonation nanodiamond particles tend to have a higher proportion of ketone groups C ⁇ O or C ⁇ O in lactones or acid anhydride groups than C—H, and are in an oxidized state. In this case, the proton of the carboxyl group is released in the aqueous solution, and the surface of the nanodiamond particles is negatively charged. Therefore, it can be said that the zeta potential in the nanodiamond particles is negative (negative).
  • the zeta potential in the nanodiamond particles is negative, it means that the oxidation has progressed, and the surface of the nanodiamond that has undergone oxidation is stable without reaction in a high temperature / oxygen atmosphere, and the heating of the resin Deterioration and thickening during processing can be suppressed.
  • the negative zeta potential in the detonation nanodiamond particles means that the zeta potential at pH 7 at 25 ° C. measured by, for example, laser Doppler electrophoresis is negative.
  • the zeta potential is, for example, ⁇ 60 to ⁇ 5 mV, preferably ⁇ 50 to ⁇ 10 mV, and more preferably ⁇ 40 to ⁇ 15 mV.
  • the details of the laser Doppler electrophoresis method are as described in the examples of the present application.
  • the zeta potential can be obtained by the method described in the examples of the present application.
  • the detonation nanodiamond particles in the present invention can be produced by a method including at least the following production process and purification process. Depending on the nanodiamond particles to be used, the following alkaline perwater treatment, oxygen oxidation step (vapor phase oxidation), and hydrogenation step may be included as necessary.
  • nanodiamonds are produced by the detonation method. Specifically, first, a molded explosive equipped with an electric detonator is installed inside a pressure-resistant container for detonation, and in a state where a predetermined gas and a used explosive coexist in the container. To seal.
  • the container is made of, for example, iron, and the volume of the container is, for example, 0.5 to 40 m 3 .
  • the explosive a mixture of trinitrotoluene (TNT) and cyclotrimethylenetrinitroamine, ie hexogen (RDX), can be used.
  • the mass ratio of TNT to RDX is, for example, in the range of 40/60 to 60/40.
  • the amount of explosive used is, for example, 0.05 to 2.0 kg.
  • the above gas sealed in the container together with the explosive used may have an atmospheric composition or may be an inert gas.
  • the detonation method is preferably performed in an inert gas atmosphere from the viewpoint of producing nanodiamonds having a small amount of functional groups on the primary particle surface.
  • the inert gas for example, at least one selected from nitrogen, argon, carbon dioxide, and helium can be used.
  • the electric detonator is then detonated and the explosive is detonated in the container.
  • Detonation refers to an explosion associated with a chemical reaction in which the reaction flame surface moves at a speed exceeding the speed of sound.
  • the diamond used is generated by the action of the pressure and energy of the shock wave generated by the explosion, using the carbon that is liberated due to partial incomplete combustion of the explosive used.
  • the detonation method it is possible to appropriately generate nanodiamond having a primary particle size of 10 nm or less. Nanodiamond is a product obtained by the detonation method.
  • the adjacent primary particles or crystallites are very strong due to the coulomb interaction between crystal planes in addition to the action of van der Waals force. Gather and form a cohesive.
  • the temperature of the container and its interior is then lowered by leaving it at room temperature, for example, for 24 hours.
  • the nanodiamond coarse product (including the nanodiamond adherends and wrinkles produced as described above) adhering to the inner wall of the container is scraped off with a spatula, and the nanodiamond coarse product is scraped off.
  • the product is recovered.
  • a crude product of nanodiamond particles can be obtained by the detonation method as described above. Moreover, it is possible to acquire a desired amount of crude nanodiamond products by performing the above-described generation process as many times as necessary.
  • the purification step includes a pickling treatment in which a strong acid is allowed to act on the crude nanodiamond product as a raw material in, for example, an aqueous solvent.
  • the nano-diamond crude product obtained by the detonation method is likely to contain a metal oxide.
  • This metal oxide is an oxide such as Fe, Co, Ni, etc. derived from the container used for the detonation method. is there.
  • the metal oxide can be dissolved and removed from the nanodiamond crude product (pickling treatment).
  • the strong acid used for the pickling treatment is preferably a mineral acid, and examples thereof include hydrochloric acid, hydrofluoric acid, sulfuric acid, nitric acid, and aqua regia.
  • one type of strong acid may be used, or two or more types of strong acid may be used.
  • the concentration of the strong acid used in the pickling treatment is, for example, 1 to 50% by mass.
  • the pickling temperature is, for example, 70 to 150 ° C.
  • the pickling time is, for example, 0.1 to 24 hours.
  • the pickling treatment can be performed under reduced pressure, normal pressure, or increased pressure. After such pickling treatment, the solid content (including the nanodiamond adherend) is washed with water, for example, by decantation.
  • the above pickling treatment may be omitted.
  • the purification step includes a solution oxidation treatment for removing non-diamond carbon such as graphite and amorphous carbon from a nanodiamond crude product (nanodiamond aggregate before purification is finished) using an oxidizing agent.
  • the nano-diamond crude product obtained by the detonation method contains non-diamond carbon such as graphite and amorphous carbon. This non-diamond carbon causes partial incomplete combustion of the explosive used. It originates from the carbon which did not form the nano diamond crystal among the free carbon.
  • non-diamond carbon can be removed from the nanodiamond crude product by applying a predetermined oxidizing agent in an aqueous solvent, for example (solution oxidation treatment).
  • a predetermined oxidizing agent used in the solution oxidation treatment include chromic acid, chromic anhydride, dichromic acid, permanganic acid, perchloric acid, and salts thereof, nitric acid, and mixed acid (a mixture of sulfuric acid and nitric acid).
  • a mixed acid treatment using a mixed acid is preferable.
  • the ratio of concentrated sulfuric acid to concentrated nitric acid for preparing the mixed acid is, for example, 1: 1 to 10: 1 (volume ratio).
  • the solution oxidation treatment one kind of oxidizing agent may be used, or two or more kinds of oxidizing agents may be used.
  • the concentration of the oxidizing agent used in the solution oxidation treatment is, for example, 3 to 50% by mass.
  • the amount of the oxidizing agent used in the solution oxidation treatment is, for example, 300 to 2000 parts by mass with respect to 100 parts by mass of the nanodiamond crude product subjected to the solution oxidation treatment.
  • the solution oxidation treatment temperature is, for example, 50 to 250 ° C.
  • the solution oxidation treatment time is, for example, 1 to 72 hours.
  • the solution oxidation treatment can be performed under reduced pressure, normal pressure, or increased pressure.
  • the solid content (including the nanodiamond adherend) is washed with water, for example, by decantation.
  • water for example, by decantation.
  • the supernatant liquid at the beginning of water washing is colored, it is preferable to repeat the washing of the solid content by decantation until the supernatant liquid becomes transparent visually.
  • detonation nanodiamond particles are obtained as a dry powder by subjecting the obtained slurry to a drying treatment.
  • a mixed acid treatment using a mixed acid is preferable from the viewpoint of increasing the degree of purification of nanodiamond when it is subjected to an oxygen oxidation step (gas phase oxidation) described later.
  • the ratio (volume ratio) of concentrated sulfuric acid and concentrated nitric acid for preparing the mixed acid is preferably 1: 1 to 10: 1, more preferably 2: 1 to 9: 1, more preferably 3: 1 to 8: 1.
  • the mixed acid treatment temperature is preferably 80 to 200 ° C., more preferably 100 to 190 ° C., more preferably 120 to 180 ° C.
  • the mixed acid treatment time is preferably 1 to It is 96 hours, more preferably 5 to 84 hours, and more preferably 10 to 72 hours.
  • At least one of the pickling treatment and the solution oxidation treatment may be performed, or both may be performed. Moreover, when performing both, a solution oxidation process may be performed after a pickling process, and a pickling process may be performed after a solution oxidation process.
  • the alkali used for the alkaline water treatment examples include sodium hydroxide, ammonia, potassium hydroxide and the like.
  • the alkali concentration is, for example, 0.1 to 10% by mass
  • the hydrogen peroxide concentration is, for example, 1 to 15% by mass
  • the treatment temperature is, for example, 40 to 100 ° C.
  • the treatment time is, for example, 0. .5-5 hours.
  • the alkaline overwater treatment can be performed under reduced pressure, normal pressure, or increased pressure.
  • the metal impurities remaining in the nanodiamond may be removed by applying a predetermined strong acid as necessary.
  • the acid used for this treatment include sulfuric acid and hydrochloric acid.
  • an oxygen oxidation step (gas phase oxidation) may be performed.
  • the nanodiamond powder that has undergone the purification step is heated in a gas atmosphere having a predetermined composition containing oxygen using a gas atmosphere furnace.
  • nano-diamond powder is disposed in a gas atmosphere furnace, oxygen-containing gas is supplied to or passed through the furnace, and the furnace is heated to a temperature condition set as a heating temperature.
  • Oxygen oxidation treatment gas phase oxidation
  • the temperature condition of this oxygen oxidation treatment is, for example, 250 to 500 ° C.
  • the lower limit of the temperature condition for the oxygen oxidation treatment is preferably 280 ° C, more preferably 320 ° C.
  • the upper limit of the temperature condition of the oxygen oxidation treatment is preferably 450 ° C., more preferably 400 ° C.
  • the oxygen-containing gas is a mixed gas containing an inert gas and oxygen.
  • the inert gas include nitrogen, argon, carbon dioxide, and helium.
  • the oxygen content of the mixed gas, that is, the oxygen concentration, is preferably 1 to 35% by volume, more preferably 1 to 10% by volume, and more preferably 2 to 5% by volume.
  • a hydrogenation step may be performed.
  • the nanodiamond powder that has undergone the oxygen oxidation step (vapor phase oxidation) is heated in a gas atmosphere of a predetermined composition containing hydrogen using a gas atmosphere furnace.
  • a hydrogen-containing gas is supplied to or passed through a gas atmosphere furnace in which nanodiamond powder is arranged, and the temperature in the furnace is increased to a temperature condition set as a heating temperature. Processing is performed.
  • the temperature condition for this hydrogenation treatment is 400 to 800 ° C., for example.
  • the lower limit of the temperature condition of the hydrotreatment is preferably 500 ° C, more preferably 550 ° C.
  • the upper limit of the temperature condition of the hydrogenation treatment is preferably 700 ° C, more preferably 650 ° C.
  • the hydrogen-containing gas is a mixed gas containing an inert gas and hydrogen.
  • the inert gas include nitrogen, argon, carbon dioxide, and helium.
  • the hydrogen content of the mixed gas, that is, the hydrogen concentration is, for example, 0.1 to 99.9% by volume, preferably 0.5 to 50% by volume, more preferably 1 to 10% by volume.
  • the metal content is 3000 ppm or less, and the maximum absorption peak at 1700 to 1850 cm ⁇ 1 is 2800 to 3000 cm ⁇ in the infrared absorption spectrum by a Fourier transform infrared spectrophotometer (FT-IR). Detonated nanodiamond particles characterized by being higher than the absorption peak of 1 can be produced.
  • FT-IR Fourier transform infrared spectrophotometer
  • the resin composition of the present invention includes the resin additive and a resin.
  • the resin include a thermoplastic resin and a thermosetting resin.
  • a thermoplastic resin is preferable.
  • the resin composition may contain one type of resin or two or more types of resins.
  • the resin composition of the present invention is in the form of a pellet that is a resin molding raw material, a form that is softened or melted from the form of the resin molding raw material, and a form of a resin molded body that is formed through a softened or molten state. It can take.
  • thermoplastic resin examples include aromatic polyether ketone, polyphenylene sulfide (melting point 280 ° C., glass transition temperature 90 ° C.), polyether sulfone (glass transition temperature 225 ° C.), polyarylate (glass transition temperature 275 ° C.), Polyamideimide (glass transition temperature 275 ° C.), thermoplastic polyimide (glass transition temperature 250 ° C.), polybenzimidazole (glass transition temperature 427 ° C.), polyamide 9T (melting point 306 ° C., glass transition temperature 125 ° C.) and the like.
  • the thermoplastic resin preferably contains an aromatic polyether ketone or polyphenylene sulfide.
  • aromatic polyether ketone examples include polyether ketone (melting point 373 ° C., glass transition temperature 140 ° C.), polyether ether ketone (melting point 334 ° C., glass transition temperature 143 ° C.), polyether ketone ketone (melting point 396 ° C., Glass transition temperature 165 ° C.), polyether ether ketone ketone (melting point 360 ° C., glass transition temperature 149 ° C.) and the like.
  • the glass transition temperature of the thermoplastic resin is, for example, 220 ° C. or higher, preferably 230 ° C. or higher, more preferably 240 ° C. or higher, more preferably 250 ° C. or higher.
  • the upper limit of the glass transition temperature is, for example, 400 ° C.
  • the glass transition temperature is a value measured by differential scanning calorimetry (DSC) in accordance with JIS standards (JIS K 7121: plastic transition temperature measurement method).
  • the resin content in the resin composition is, for example, 80 to 99.999% by mass, preferably 90 to 99.9% by mass, and more preferably 95 to 99.6% by mass.
  • the content of the resin additive in the resin composition is, for example, 0.1 to 20% by mass, preferably 0.2 to 10% by mass, and more preferably 0.3 to 5% by mass.
  • the content of the resin additive with respect to 100 parts by mass of the resin is, for example, 0.001 to 5 parts by mass.
  • the lower limit of the content of the resin additive is preferably 0.002 parts by mass, more preferably 0.01 parts by mass, and more preferably 0.1 parts by mass.
  • the upper limit of the content of the resin additive is preferably 3.0 parts by mass, more preferably 2.0 parts by mass, and more preferably 1.0 parts by mass. As the content of the resin additive is increased, for example, a greater effect as a radical stabilizer is obtained. However, when the content exceeds the upper limit of the content, no further effect is obtained.
  • the resin composition may contain other components in addition to the resin and the additive for resin.
  • other components include flame retardants, glass fibers, carbon fibers, antistatic agents, lubricants, and colorants.
  • the resin composition is prepared by mixing (mixing) pellets as a raw material of resin, detonation nanodiamond particles as a dry powder, and other components added as necessary, using a mixer. Step), and then kneaded with heat using a kneader (kneading step).
  • the mixer include a Henschel mixer, a tumbler, and a revolution mill.
  • the kneader include a batch type polymer mixer, a twin screw extruder, a single screw extruder, a Banbury mixer, and a roll mixer.
  • the kneaded material obtained by the above process may be molded into a predetermined shape, or the kneaded material may be pelletized, or the obtained pellets may be injection molded from the raw material.
  • Example 1 Production of nanodiamond (ND1)
  • purification process 1 oxidation treatment with chromic acid
  • alkaline perwater treatment process purification process 2 (acid treatment)
  • drying process dry nanodiamond powder (ND1) was produced.
  • a molded explosive with an electric detonator was installed inside a pressure-resistant container for detonation, and the container was sealed.
  • the container is made of iron and the volume of the container is 15 m 3 .
  • As the explosive 0.50 kg of a mixture of trinitrotoluene (TNT) and cyclotrimethylenetrinitroamine or hexogen (RDX) was used.
  • the mass ratio (TNT / RDX) of TNT and RDX in the explosive is 50/50.
  • the electric detonator was detonated, and the explosive was detonated in the container.
  • the container and its interior were cooled by being left at room temperature for 24 hours.
  • the nanodiamond crude product (including the nanodiamond particle aggregates and soot produced by the above detonation method) adhering to the inner wall of the container is scraped off with a spatula.
  • the crude product was recovered.
  • Alkaline overwater treatment process After adding 1 L of 10% by mass sodium hydroxide aqueous solution and 1 L of 30% by mass hydrogen peroxide aqueous solution to the precipitate after the decantation to form a slurry, the slurry is subjected to reflux under normal pressure conditions. Heat treatment for 1 hour was performed. The heating temperature in this alkaline overwater treatment is 50 to 105 ° C. Next, after cooling, the supernatant was removed by decantation.
  • the electrical conductivity was measured using an electrical conductivity measuring device (trade name “TWIN-COND B-771”, manufactured by Horiba, Ltd.). The measurement temperature is 25 ° C.
  • a drying process was performed. Specifically, the nanodiamond dispersion obtained as described above is spray-dried using a spray dryer (trade name “Spray Dryer B-290”, manufactured by Nihon Büch) to form a powder. did. As described above, a dry powder (ND1) of nanodiamond was produced.
  • the obtained nanodiamond dry powder (ND1) was subjected to solid state 13 C-NMR analysis, FT-IR measurement, and zeta potential measurement by the following measurement methods.
  • solid state 13 C-NMR analysis the proportion of each carbon atom is 9.4% of hydroxyl-bonded carbon (C—OH) and carboxyl carbon (C ( ⁇ O) O) with respect to the total carbon atoms contained in the nanodiamond. ) was 0.4%, hydrogen-bonded carbon was 13.1%, and sp 3 carbon was 77.0%.
  • FT-IR as shown in FIG.
  • Nanodiamond (ND2) was produced in the same manner as in Example 1 except that the purification step 2 (acid treatment) in Example 1 was not performed.
  • the obtained nanodiamond dry powder (ND2) was subjected to FT-IR measurement and zeta potential measurement by the following measurement methods.
  • Absorption peak of 1753 cm -1 was higher than the absorption peak of 2931cm -1.
  • the zeta potential was ⁇ 28 mV (25 ° C., pH 7).
  • Example 2 Production Example 2 of nanodiamond (ND3)
  • Nanodiamond (ND3) was prepared in the same manner as in Example 1 except that the following purification step 1 ′ (oxidation treatment with mixed acid) was performed instead of the purification step 1 (oxidation treatment with chromic acid) in Example 1 above.
  • the obtained nanodiamond dry powder (ND3) was subjected to FT-IR measurement and zeta potential measurement by the following measurement methods. In FT-IR, as shown in FIG.
  • Example 3 Production of nanodiamond (ND4)
  • the following gas phase oxidation 1 was performed to produce nanodiamond (ND4).
  • the obtained nanodiamond dry powder (ND4) was subjected to solid state 13 C-NMR analysis, FT-IR measurement, and zeta potential measurement by the following measurement methods.
  • solid state 13 C-NMR analysis the proportion of each carbon atom is 14.7% of hydroxyl-bonded carbon (C—OH) and carboxyl carbon (C ( ⁇ O) O) with respect to the total carbon atoms contained in the nanodiamond.
  • carbonyl carbon (C ⁇ O) was 0.4%
  • hydrogen-bonded carbon was 14.4%
  • sp 3 carbon was 70.0%.
  • the thermal oxidation process was performed using a gas atmosphere furnace (trade name “Gas Atmosphere Tube Furnace KTF045N1”, manufactured by Koyo Thermo Systems Co., Ltd.). Specifically, 4.5 g of the nanodiamond powder obtained as described above was placed in the core tube of a gas atmosphere furnace, and nitrogen gas was continuously passed through the core tube at a flow rate of 1 L / min for 30 minutes. Thereafter, the flow gas was switched from nitrogen to a mixed gas of oxygen and nitrogen, and the mixed gas was continuously passed through the reactor core tube at a flow rate of 1 L / min. The oxygen concentration in the mixed gas is 4% by volume.
  • the temperature in the furnace was raised to a heating set temperature of 400 ° C.
  • the heating rate was 10 ° C./min from 380 ° C., which is 20 ° C. lower than the heating set temperature, and then 1 ° C./min from 380 ° C. to the heating set temperature.
  • the oxygen oxidation process was performed about the nano diamond powder in a furnace, maintaining the temperature conditions in a furnace at 400 degreeC.
  • the processing time was 3 hours. As described above, the nanodiamond powder of Example 3 that had undergone the thermal oxidation process or oxygen oxidation treatment was obtained.
  • the ratio (yield) of the amount of nanodiamond powder after the thermal oxidation step or oxygen oxidation treatment to the amount of nanodiamond powder before being subjected to the thermal oxidation step or oxygen oxidation treatment was determined to be 95%. Met.
  • Example 4 Production Example 2 of Nano Diamond (ND5)
  • ND5 nanodiamond dry powder
  • FT-IR FT-IR
  • zeta potential measurement by the following measurement methods.
  • FT-IR as shown in FIG. 5, an absorption peak derived from C ⁇ O of the lactone or acid anhydride group in the surface functional group was observed near 1800 cm ⁇ 1 .
  • a conspicuous absorption peak was not observed at 2800 to 3000 cm ⁇ 1 .
  • the zeta potential was ⁇ 33 mV (25 ° C., pH 7).
  • Example 4 (Gas phase oxidation 2) A nanodiamond powder of Example 4 was obtained in the same manner as in Gas Phase Oxidation 1 except that the heating set temperature in Gas Phase Oxidation 1 of Example 3 was changed to 475 ° C. The rate of temperature increase was 10 ° C./min up to 455 ° C., 20 ° C. lower than the heating set temperature, and then 1 ° C./min from 455 ° C. to the heating set temperature. The ratio (yield) of the amount of nanodiamond powder after the thermal oxidation step or oxygen oxidation treatment to the amount of nanodiamond powder before being subjected to the thermal oxidation step or oxygen oxidation treatment was found to be 69%. Met.
  • the gas to be ventilated was switched from hydrogen to nitrogen and vented overnight. The next morning, the aeration of nitrogen gas was stopped, the quartz boat was taken out from the tubular furnace, and the sample was collected. The weight after recovery was 1.35 g.
  • FT-IR measurement> A Fourier transform infrared spectrophotometer, a product name “FT-720” (manufactured by Horiba Seisakusho Co., Ltd.) with a heating vacuum stirring reflection Heat Chamber Type-1000 ° C. (manufactured by ST Japan Ltd.) It measured using. In order to remove the adsorbed water of the nanodiamond, FT-IR measurement was performed after heating at 150 ° C. for 1 minute under a degree of vacuum of 2 ⁇ 10 ⁇ 3 Pa.
  • Solid state 13 C-NMR analysis was performed by a solid state NMR method using a solid state NMR apparatus (trade name “CMX-300 Infinity”, manufactured by Chemicals).
  • the measurement method and other conditions related to the measurement are as follows.
  • Measurement method DD / MAS method Measurement nuclear frequency: 75.188829 MHz ( 13 C nucleus) Spectral width: 30.003 kHz Pulse width: 4.2 ⁇ sec (90 ° pulse) Pulse repetition time: ACQTM 68.26msec, PD 15sec Observation point: 2048 (data point: 8192) Reference substance: Polydimethylsiloxane (external standard: 1.56 ppm) Temperature: Room temperature (about 22 ° C) Sample rotation speed: 8.0 kHz
  • the zeta potential relating to the nanodiamond particles contained in the nanodiamond dispersion is a value measured by a laser Doppler electrophoresis method using an apparatus (trade name “Zetasizer Nano ZS”) manufactured by Spectris.
  • the nanodiamond dispersion liquid subjected to the measurement was diluted with ultrapure water to a nanodiamond concentration of 0.2% by mass and then subjected to ultrasonic irradiation with an ultrasonic cleaner.
  • the pH of the nanodiamond dispersion liquid subjected to the measurement is a value confirmed using a pH test paper (trade name “Three Band pH Test Paper”, manufactured by ASONE Corporation).
  • Example 1 shows the results of the measured content (mass) of each metal element.
  • the unit of content (mass) of each metal element in Table 1 is ppm ( ⁇ g / g).
  • ⁇ 50 means 50 ppm or less (maximum 50 ppm).
  • ⁇ Measurement of metal content 100 mg of dry matter (powder) remaining after evaporation of water from the nanodiamond dispersion or nanodiamond-containing solution by heating was subjected to dry decomposition in an electric furnace in a state of being placed in a magnetic crucible.
  • This dry decomposition was performed in three stages under the conditions of 450 ° C. for 1 hour, followed by 550 ° C. for 1 hour, and then 650 ° C. for 1 hour. After such dry decomposition, the residue in the magnetic crucible was evaporated to dryness by adding 0.5 ml of concentrated sulfuric acid to the magnetic crucible.
  • the obtained dried product was finally dissolved in 20 ml of ultrapure water.
  • an analytical sample was prepared.
  • This analysis sample was subjected to ICP emission spectroscopic analysis using an ICP emission spectroscopic analyzer (trade name “CIROS120”, manufactured by Rigaku Corporation).
  • the analysis sample was prepared so that the lower limit of detection of this analysis was 50 mass ppm.
  • SPEX mixed standard solution XSTC-22, Kanto Chemical Atomic Absorption Standard Solution K1000, and Na1000 are appropriately used in a sulfuric acid aqueous solution having the same concentration as the sulfuric acid concentration of the analysis sample. Diluted and used.
  • the measurement value obtained by operating and analyzing in the same manner with an empty crucible was subtracted from the measurement value of the nanodiamond dispersion liquid sample to be measured to obtain the metal concentration in the sample.
  • the metal (element) content in Example 1 is 547 ppm at the maximum and 397 ppm at the minimum from the total of each measured metal (element).
  • the metal (element) content in Comparative Example 1 is 4960 ppm at the maximum and 4910 ppm at the minimum from the total of the measured metals (elements).
  • the metal (element) content in Example 2 is 570 ppm from the total of the measured metals (elements).
  • the nanodiamond particles of Examples 3 and 4 are obtained by vapor-phase oxidation of the nanodiamond particles of Example 2, and it is considered that there is no change in the metal element content in the gas-phase oxidation.
  • the metal element content in 4 is considered to be comparable to that in Example 2.
  • Examples 5 to 8 and Comparative Examples 3 to 6 100 parts by mass of polyetheretherketone (PEEK) (trade name “Vesta Keep L4000G”, manufactured by Daicel Evonik Co., Ltd.) and 0.5 mass of the additive manufactured in Examples 1 to 4 and Comparative Examples 1 and 2 shown in Table 1 below
  • the mixture (total amount 30 g) was kneaded using a kneading / extrusion molding evaluation test apparatus (trade name “Laboplast Mill R-30”, kneading chamber volume 30 cc, manufactured by Toyo Seiki Seisakusho) to obtain a resin composition I got a thing.
  • the kneading temperature was 400 ° C.
  • the number of rotations of the rollers in the kneading chamber was 60 rpm
  • the kneading time was 15 minutes.
  • the complex viscosity measurement was performed by the method shown below.
  • IRANOX 1010 shown in Table 2 is a hindered phenol compound (trade name “IRGANOX 1010FF”, manufactured by BASF).
  • IRGANOX 1010FF hindered phenol compound
  • Comparative Example 3 30 g of PEEK was measured without adding anything.
  • metal content is not more than 3000 ppm, in the infrared absorption spectrum by Fourier transform infrared spectroscopy (FT-IR), the maximum peak of the absorption peak of 1700 ⁇ 1850 cm -1 it is of 2800 ⁇ 3000 cm -1
  • Additive for resin using detonation nano diamond particles which is higher than absorption peak.
  • the resin additive according to [1] wherein the sodium content of the detonation nanodiamond particles is 2000 ppm or less.
  • the additive for resin according to [1] or [2] which is a heat stabilizer and / or an antioxidant.
  • the additive for resin of the present invention has high heat resistance, can exhibit functions such as scavenging radicals even at a high processing temperature, and can suppress deterioration and thickening during heat processing of the resin. It is suitable as an additive (for example, heat stabilizer, antioxidant) for resins having a high melting point such as engineering plastics and super engineering plastics.

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  • Crystallography & Structural Chemistry (AREA)
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Abstract

La présente invention vise à procurer : un additif pour résines, qui peut empêcher la détérioration et l'épaississement d'une résine pendant une mise en œuvre thermique, qui peut faire preuve de fonctions comportant une fonction de piégeage de radicaux même à une température élevée de mise en œuvre (p.ex. 280 °C ou plus), et qui possède une grande résistance à la chaleur ; et une composition de résine comprenant l'additif pour résines et une résine. L'additif pour résines selon la présente invention est caractérisé par l'utilisation de particules de nanodiamant élaborées par détonation, qui possèdent une teneur en métal de 3000 ppm ou moins, et dont le pic maximal, parmi les pics d'absorption à 1700 à 1850 cm-1, est plus élevé que les pics d'absorption à 2800 à 3000 cm-1 dans les spectres d'absorption de rayons infrarouges, tels que mesurés par spectroscopie infrarouge avec transformation de Fourier (FT-IR).
PCT/JP2017/038500 2016-10-28 2017-10-25 Additif destiné à des résines, et composition de résine WO2018079597A1 (fr)

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