WO2019240013A1 - Composition - Google Patents

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Publication number
WO2019240013A1
WO2019240013A1 PCT/JP2019/022585 JP2019022585W WO2019240013A1 WO 2019240013 A1 WO2019240013 A1 WO 2019240013A1 JP 2019022585 W JP2019022585 W JP 2019022585W WO 2019240013 A1 WO2019240013 A1 WO 2019240013A1
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Prior art keywords
liquid crystal
crystal polymer
weight
antioxidant
particles
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PCT/JP2019/022585
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English (en)
Japanese (ja)
Inventor
梅本浩一
劉明
伊藤久義
久米篤史
田口吉昭
池田聡
Original Assignee
株式会社ダイセル
ポリプラスチックス株式会社
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Priority to JP2020525506A priority Critical patent/JP7304853B2/ja
Publication of WO2019240013A1 publication Critical patent/WO2019240013A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/44—Polyester-amides
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/12—Polyester-amides

Definitions

  • the present invention relates to a composition comprising a liquid crystal polymer and nanodiamond particles.
  • Patent Document 1 describes a heat-resistant thermoplastic composition containing a thermoplastic elastomer and an antioxidant.
  • an aromatic amine-based antioxidant As the antioxidant, an aromatic amine-based antioxidant, a hindered phenol-based antioxidant, a sulfur It describes that a system antioxidant, a phosphorus antioxidant, etc. can be used.
  • the liquid crystal polymer has a high melting point of 300 ° C. or higher, and can stably maintain its shape even in a high temperature environment (for example, a high temperature environment of 150 ° C. or higher and lower than 300 ° C.) It is possible to suppress the occurrence and maintain the shape with high accuracy). That is, it is excellent in heat resistance.
  • the liquid crystal polymer in order to mold the liquid crystal polymer, it is necessary to heat at a temperature higher than the melting point of the liquid crystal polymer.
  • the liquid crystal polymer is easily oxidized and deteriorated by heating at a temperature higher than the melting point. This is because even if an antioxidant is added to the liquid crystal polymer, the antioxidant is volatilized or thermally decomposed by high-temperature heating during molding, and the desired effect cannot be obtained.
  • an object of the present invention is to provide a composition comprising a liquid crystal polymer and an antioxidant having excellent heat resistance.
  • Another object of the present invention is to provide an antioxidant having heat resistance at a temperature equal to or higher than the molding temperature of the liquid crystal polymer.
  • the inventors of the present invention have excellent heat resistance and do not volatilize or decompose even when heated to 400 ° C. in an oxygen atmosphere. It has been found that when nanodiamond particles are added to a liquid crystal polymer, the nanodiamond particles trap peroxy radicals, thereby preventing oxidative degradation of the liquid crystal polymer in a high temperature environment.
  • the present invention has been completed based on these findings.
  • liquid crystal polymer selected from liquid crystal polyester and liquid crystal polyester amide and nanodiamond particles are added in an amount of 0.001 to 5 parts by weight of nanodiamond particles with respect to 100 parts by weight of the liquid crystal polymer.
  • Compositions containing in proportions are provided.
  • the present invention also provides the composition, wherein the liquid crystal polymer has the following constitution.
  • the content of the structural unit represented by the following formula (I) is 50 to 100 mol%
  • the content of the structural unit represented by the following formula (II) is 0 to 25 mol%
  • the content of the structural unit represented by the following formula (III) is 0 to 25 mol% (Wherein Ar 1 to Ar 3 are the same or different and may have at least one substituent selected from a halogen atom, an alkyl group, and an aryl group, a phenylene group, a naphthylene group, or biphenylylene)
  • X and Y are the same or different and represent —O— or —NH—.
  • the present invention also provides the composition, wherein the nanodiamond particles are detonation nanodiamond particles.
  • the present invention is also in the infrared absorption spectrum by Fourier transform infrared spectrophotometer of nanodiamond particles, the maximum peak of 1700 ⁇ 1850 cm -1 is provided a higher than the maximum peak of 2800 ⁇ 3000 cm -1 wherein the composition To do.
  • the present invention also provides the composition, wherein the amount of radicals generated at 320 ° C. measured by electron spin resonance is 2 ⁇ 10 16 to 2 ⁇ 10 18 spins / g.
  • the present invention also provides the composition, wherein the radical generation amount at 400 ° C. measured by an electron spin resonance method is not more than 3.0 times the radical generation amount at 25 ° C.
  • the present invention also provides a molded body comprising a solidified product of the composition.
  • the present invention also provides an antioxidant for thermoplastic resin containing nanodiamond particles.
  • the present invention also provides the antioxidant for a thermoplastic resin, wherein the 5% weight reduction temperature measured at a heating rate of 10 ° C./min (in air) is 450 ° C. or higher.
  • the composition of the present invention contains nanodiamond particles together with a liquid crystal polymer, and the nanodiamond particles exhibit an action of capturing peroxy radicals that cause oxidative deterioration of the liquid crystal polymer. Therefore, even when the composition of the present invention is heated at a high temperature, the liquid crystal polymer can be prevented from being oxidatively deteriorated, and the toughness of the liquid crystal polymer can be reduced due to the oxidative deterioration and can be prevented from becoming brittle. In addition, yellowing due to oxidative degradation can be suppressed, and the hue can be maintained well. In addition, the melt of the composition of the present invention is excellent in fluidity, has little shrinkage due to solidification, and can suppress the occurrence of warpage.
  • the molded article of the composition of the present invention suppresses deterioration of physical properties (for example, toughness, embrittlement, etc.) over a long period of time even in a high temperature environment (for example, a high temperature environment of 150 ° C. or higher and lower than 400 ° C.). be able to. Therefore, it withstands long-term use at high temperatures.
  • a high temperature environment for example, a high temperature environment of 150 ° C. or higher and lower than 400 ° C.
  • the composition of the present invention has the above-mentioned characteristics, for example, printed circuit board mounting parts, connectors / bobbins / optical pickup parts cases, micromotor parts and other electric / electronic parts materials; compressor parts, shock absorber parts and other automobiles It can be suitably used as a component material.
  • the antioxidant of the present invention contains, as a main component, nanodiamond particles having both an antioxidant effect (or peroxy radical scavenging effect) and heat resistance. Therefore, it can be suitably used as an antioxidant (or a peroxy radical scavenger) for a high melting point thermoplastic resin having a molding temperature of 300 ° C. or higher.
  • FIG. 4 is a diagram showing FT-IR data of ND1 obtained in Example 1.
  • FIG. 6 is a diagram showing FT-IR data of ND2 obtained in Example 2.
  • FIG. 6 is a diagram showing FT-IR data of ND3 obtained in Example 3.
  • FIG. 6 is a diagram showing FT-IR data of ND4 obtained in Example 4.
  • FIG. It is a correlation diagram of temperature and the amount of radical generation of the composition obtained in Example 8 and Comparative Example 1 obtained by ESR measurement.
  • composition of the present invention comprises at least one liquid crystal polymer selected from liquid crystal polyester and liquid crystal polyester amide, and nanodiamond particles (hereinafter sometimes referred to as “ND particles”) in 100 parts by weight of the liquid crystal polymer.
  • ND particles nanodiamond particles
  • the nanodiamond particles are contained at a ratio of 0.001 to 5 parts by weight with respect to the above.
  • the liquid crystal polymer in the present invention refers to a melt processable polymer having a property capable of forming an optically anisotropic melt phase.
  • the property of the anisotropic molten phase can be confirmed by a conventional polarization inspection method using an orthogonal polarizer. More specifically, the anisotropic molten phase can be confirmed by using a Leitz polarizing microscope and observing a molten sample placed on a Leitz hot stage under a nitrogen atmosphere at a magnification of 40 times.
  • the liquid crystal polymer of the present invention is inspected between crossed polarizers, the polarized light is usually transmitted and optically anisotropic even if it is in a molten stationary state.
  • the liquid crystal polymer in the present invention is at least one liquid crystal polymer selected from liquid crystal polyester and liquid crystal polyester amide.
  • liquid crystal polymer examples include at least a structural unit represented by the following formula (I) and may include a structural unit represented by the following formula (II) and / or a structural unit represented by the following formula (III).
  • a good liquid crystal polymer is mentioned.
  • Ar 1 to Ar 3 are the same or different and may have at least one substituent selected from a halogen atom, an alkyl group, and an aryl group, a phenylene group, a naphthylene group, or biphenylylene
  • X and Y are the same or different and represent —O— or —NH—.
  • halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the content of the structural unit represented by the formula (I) is, for example, 50 to 100 mol%.
  • the content of the structural unit represented by the formula (II) is, for example, 0 to 25 mol%.
  • the content of the structural unit represented by the formula (III) is, for example, 0 to 25 mol%.
  • the total content is, for example, 70 mol% or more, preferably 80 mol% or more, particularly preferably 90 mol% or more.
  • the content of the structural unit represented by the following formula (VI) is preferably, for example, 30 mol% or less, more preferably 20 mol% or less, based on all the structural units constituting the liquid crystal polymer. Especially preferably, it is 10 mol% or less, Most preferably, it is 5 mol% or less, Most preferably, it is 1 mol% or less.
  • content of the structural unit shown by following formula (VI) exceeds the said range, there exists a tendency for the antioxidant effect by ND particle
  • Ar 4 to Ar 6 are the same or different and each may have at least one substituent selected from a halogen atom, an alkyl group, and an aryl group, a phenylene group, a naphthylene group, or biphenylylene) Group
  • examples of the liquid crystal polymer include the following embodiments (1) to (5). Furthermore, you may use a molecular weight modifier together with the following structural component as needed.
  • the monomer constituting the liquid crystal polymer include aromatic hydroxycarboxylic acids such as p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid; 2,6-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 4 Aromatic diols such as, 4'-dihydroxybiphenyl, hydroquinone, resorcin; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 4,4'-diphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid; p-aminophenol, and aromatic amines such as p-phenylenediamine.
  • aromatic hydroxycarboxylic acids such as p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid
  • 2,6-dihydroxynaphthalene 1,4-dihydroxynaphthalene
  • 4 Aromatic diols such as, 4'-dihydroxybi
  • the liquid crystal polymer is not particularly limited and can be prepared by a known method, and examples thereof include a direct polymerization method and a transesterification method.
  • the monomer or monomer mixture
  • the direct polymerization method the monomer (or monomer mixture) is melt-polymerized, solution-polymerized, slurry-polymerized, solid-phase polymerized, or a combination of two or more of these (preferably, melt-polymerized or melt-polymerized In combination with a solid phase polymerization method).
  • the monomer when the monomer is a compound having ester forming ability, it can be used for polymerization as it is, but when the monomer is a compound having no ester forming ability, an acylating agent (for example, It is preferable to use a derivative modified with a derivative having ester-forming ability using carboxylic anhydride such as acetic anhydride).
  • an acylating agent for example, It is preferable to use a derivative modified with a derivative having ester-forming ability using carboxylic anhydride such as acetic anhydride).
  • the polymerization of the monomer is preferably performed in the presence of a catalyst.
  • the catalyst include metal salt catalysts and organic compound catalysts. These can be used alone or in combination of two or more.
  • metal salt catalyst examples include potassium acetate, magnesium acetate, stannous acetate, tetrabutyl titanate, lead acetate, sodium acetate, antimony trioxide, tris (2,4-pentanedionato) cobalt (III), etc. Is mentioned.
  • organic compound catalyst examples include N-methylimidazole and 4-dimethylaminopyridine.
  • the amount of the catalyst used is, for example, about 0.0001 to 0.01 parts by weight with respect to 100 parts by weight of the monomer.
  • the polymerization temperature of the monomer is, for example, 200 to 400 ° C.
  • the atmosphere during the polymerization reaction of the monomer is not particularly limited as long as the reaction is not inhibited, and may be any of an air atmosphere, a nitrogen atmosphere, an argon atmosphere, and the like.
  • the polymerization reaction of the monomer can be performed under reduced pressure, normal pressure, or increased pressure.
  • the liquid crystal polymer obtained by the above method can be further increased in molecular weight by solid phase polymerization heated in an inert gas.
  • the heating temperature is, for example, 230 to 350 ° C., preferably 260 to 330 ° C.
  • the final ultimate pressure is, for example, 10 to 760 Torr (that is, 1330 to 101080 Pa).
  • the melting point or softening point of the liquid crystal polymer is, for example, 250 ° C. or higher, preferably 270 ° C. or higher.
  • the upper limit of the melting point or softening point of the liquid crystal polymer is 400 ° C., for example.
  • the melt viscosity measured under conditions of a shear rate of 1000 sec ⁇ 1 at a cylinder temperature 10 to 30 ° C. higher than the melting point or softening point of the liquid crystal polymer is, for example, 5 to 100 Pa ⁇ s, preferably 10 to 60 Pa ⁇ s, particularly preferably 15 to 50 Pa ⁇ s.
  • the “cylinder temperature 10-30 ° C. higher than the melting point or softening point of the liquid crystal polymer” means a cylinder temperature at which the liquid crystal polymer can be melted to such an extent that the melt viscosity can be measured.
  • the number of degrees C higher than the melting point or softening point can be appropriately selected depending on the type of the liquid crystal polymer within the temperature range (that is, within the range of 10 to 30 ° C.).
  • the primary particle diameter (D50, median diameter) of ND particles is 10 nm or less, preferably 8 nm or less, particularly preferably 7 nm or less, and most preferably 6 nm or less.
  • the lower limit of the particle size of the ND particles is, for example, 2 nm.
  • the ND particles have a carbonyl group (C ⁇ O group) on the surface in terms of being excellent in an antioxidant effect (particularly, an antioxidant effect of a liquid crystal polymer).
  • the ND particles in the present invention may have other functional groups (for example, C—H groups) in addition to carbonyl groups on the surface, but may have more carbonyl groups than other functional groups. preferable.
  • the surface functional group of the ND particle can be confirmed by an infrared absorption spectrum.
  • 1700 tallest peak at ⁇ 1850 cm -1 e.g., P1 in Fig. 1
  • the maximum peak of 2800 ⁇ 3000 cm -1 e.g., P2 in Fig. 1 is higher than
  • (details the absorption peak derived from C O near 1712 cm -1, absorption peaks were observed originating from C-H in the vicinity of 2915 cm -1
  • absorption peaks of 1712 cm -1 is than the absorption peak of 2915 cm -1
  • the infrared absorption spectrum can be measured using FTIR [Fourier transform infrared spectrophotometer; FT / IR-4200 type A (manufactured by JASCO Corporation)].
  • the ND particles can be produced, for example, by the detonation method described in detail below, but the ND particles in the present invention are not limited to those produced by this method.
  • a molded explosive with an electric detonator is installed inside a pressure-resistant container for detonation, and the container is sealed in a state where atmospheric pressure gas and atmospheric explosive coexist in the container.
  • the container is made of, for example, iron, and the volume of the container is, for example, 0.5 to 40 m 3 .
  • As the explosive a mixture of trinitrotoluene (TNT) and cyclotrimethylenetrinitroamine, ie hexogen (RDX), can be used.
  • TNT / RDX The weight ratio of TNT to RDX (TNT / RDX) is, for example, in the range of 40/60 to 60/40.
  • 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.
  • ND particles are generated by the action of the pressure and energy of the shock wave generated by the explosion, using as a raw material carbon that has been partially incompletely burned by the explosive used.
  • the produced ND particles are aggregated very strongly as a result of coulomb interaction between crystal planes in addition to the action of van der Waals force between adjacent primary particles or crystallites to form an aggregate.
  • the container and the interior thereof are then allowed to cool by allowing to stand at room temperature for about 24 hours and allowing to cool.
  • the ND particle crude product adhering to the inner wall of the container (including the ND particle aggregates and soot generated as described above) is scraped off with a spatula and collected.
  • a crude product of ND particles can be obtained by the method as described above.
  • the acid treatment step is a step of removing metallic impurities mixed in the crude product of ND particles obtained through the production step, and the crude product of ND particles obtained by dispersing the crude product of ND particles in water.
  • an acid to the product dispersion to elute the metallic impurities into the acid, and then separating and removing the acid from which the metallic impurities are eluted, the metallic impurities can be removed.
  • a mineral acid is preferable, and examples thereof include hydrochloric acid, hydrofluoric acid, sulfuric acid, nitric acid, aqua regia and the like. These can be used individually by 1 type or in combination of 2 or more types.
  • the concentration of the acid used for the acid treatment is, for example, 1 to 50% by weight.
  • the acid treatment temperature is, for example, 70 to 150 ° C.
  • the acid treatment time is, for example, 0.1 to 24 hours.
  • the acid treatment can be performed under reduced pressure, normal pressure, or increased pressure.
  • decantation it is preferable to wash the solids (including ND particles) with water, and it is particularly preferable to repeat the water washing until the pH of the precipitate reaches, for example, 2 to 3.
  • the oxidation treatment step is a step of removing graphite from the ND particle crude product using an oxidizing agent.
  • the crude product of ND particles obtained by the detonation method includes graphite (graphite), but this graphite does not form ND particle crystals out of the carbon released by partial incomplete combustion of the explosive used. Derived from carbon.
  • graphite can be removed from the ND particle crude product by applying a predetermined oxidizing agent in an aqueous solvent.
  • an oxygen-containing group such as a carboxyl group or a hydroxyl group can be introduced to the surface of the ND particle by causing an oxidant to act.
  • Examples of the oxidizing agent used in this oxidation treatment include chromic acid, chromic anhydride, dichromic acid, permanganic acid, perchloric acid, nitric acid, and mixtures thereof, and at least one acid selected from these. And mixed acids of these with other acids (for example, sulfuric acid), and salts thereof.
  • a mixed acid particularly, a mixed acid of sulfuric acid and nitric acid because it is environmentally friendly and excellent in oxidizing and removing graphite.
  • the mixing ratio of sulfuric acid and nitric acid in the mixed acid is, for example, 60/40 to 95/5, even under a pressure around normal pressure (for example, 0.5 to 2 atm).
  • graphite can be efficiently oxidized and removed at a temperature of 130 ° C. or higher (particularly preferably 150 ° C. or higher, and the upper limit is, for example, 200 ° C.).
  • the lower limit of the mixing ratio is preferably 65/35, particularly preferably 70/30.
  • the upper limit of the mixing ratio is preferably 90/10, particularly preferably 85/15, and most preferably 80/20.
  • the ratio of nitric acid in the mixed acid exceeds the above range, the content of sulfuric acid having a high boiling point is decreased. Therefore, the reaction temperature becomes, for example, 120 ° C. or less under a pressure near normal pressure, and the graphite removal efficiency tends to decrease. There is.
  • the ratio of nitric acid in the mixed acid is less than the above range, the content of nitric acid that greatly contributes to the oxidation of graphite is reduced, so that the graphite removal efficiency tends to decrease.
  • the amount of the oxidizing agent (especially the mixed acid) used is, for example, 10 to 50 parts by weight, preferably 15 to 40 parts by weight, and particularly preferably 20 to 40 parts by weight with respect to 1 part by weight of the ND particle crude product.
  • the amount of sulfuric acid used in the mixed acid is, for example, 5 to 48 parts by weight, preferably 10 to 35 parts by weight, particularly preferably 15 to 30 parts by weight, based on 1 part by weight of the ND particle crude product.
  • the amount of nitric acid used in the mixed acid is, for example, 2 to 20 parts by weight, preferably 4 to 10 parts by weight, particularly preferably 5 to 8 parts by weight, based on 1 part by weight of the ND particle crude product.
  • a catalyst may be used together with the mixed acid.
  • the graphite removal efficiency can be further improved.
  • the catalyst include copper (II) carbonate.
  • the amount of the catalyst used is, for example, about 0.01 to 10 parts by weight with respect to 100 parts by weight of the ND particle crude product.
  • the oxidation treatment temperature is 100 to 200 ° C., for example.
  • the oxidation treatment time is, for example, 1 to 24 hours.
  • the oxidation treatment can be performed under reduced pressure, normal pressure, or increased pressure.
  • decantation it is preferable to wash the solids with water. Although the supernatant liquid at the beginning of water washing is colored, it is preferable to repeat the water washing of the solid content until the supernatant liquid becomes transparent visually.
  • drying process it is preferable to provide a drying step next. For example, after the liquid content is evaporated from the ND particle-containing solution obtained through the above steps using a spray drying device, an evaporator, or the like, the resulting solid content is dried by heating and drying in a drying oven. A method is mentioned. The heating and drying temperature is, for example, 40 to 150 ° C. Through such a drying process, ND particles are obtained.
  • the heating oxidation step is a step of obtaining ND particles having C ⁇ O groups on the surface thereof by heating and oxidizing the ND particles obtained through the above steps in an atmosphere containing oxygen.
  • the reaction atmosphere in the heating oxidation step is not particularly limited as long as it is a gas containing oxygen.
  • oxygen diluted with an inert gas such as nitrogen from the viewpoint of safety, and the concentration of oxygen is, for example, 0.01 to 30 v / v%, preferably 0. .1 to 25 v / v%, particularly preferably 0.5 to 10 v / v%.
  • the heating temperature in the heating oxidation step can be appropriately set in consideration of the heat resistance of the ND particles, and is preferably 200 to 800 ° C., more preferably 350 to 700 ° C., further preferably 400 to 600 ° C., and particularly preferably. 430-500 ° C.
  • the heating temperature is within the above range, oxidation of ND particles is suppressed, non-diamond carbon is selectively oxidized, ND particles having a large amount of C ⁇ O groups on the surface and excellent in the antioxidant effect are obtained. It is done.
  • the heating time in the heating and oxidizing step is not particularly limited, but is preferably 0.1 to 15 hours, more preferably 0.5 to 12 hours, and still more preferably 1 to 10 hours.
  • the heating time is within the above range, oxidation of ND particles is suppressed, non-diamond carbon is selectively oxidized, ND particles having a large amount of C ⁇ O groups on the surface and excellent in the antioxidant effect are obtained. It is done.
  • the pressure in the heating oxidation step is not particularly limited, but is preferably 0.01 to 5.0 atm, more preferably 0.1 to 1.5 atm, and further preferably 0.2 to 1.2 atm.
  • composition of the present invention can be produced, for example, by melt-kneading a liquid crystal polymer and ND particles at a temperature equal to or higher than the melting point (or softening temperature) of the liquid crystal polymer.
  • the content of ND particles in the composition of the present invention is 0.001 to 5 parts by weight, preferably 0.01 to 3 parts by weight, particularly preferably 0.1 to 1 part by weight, based on 100 parts by weight of the liquid crystal polymer. Part.
  • the composition of the present invention contains a liquid crystal polymer and ND particles as nonvolatile components.
  • the composition of the present invention includes other components (for example, fillers, stabilizers, lubricants, pigments, crystal nucleating agents, antifoaming agents, silane coupling agents, leveling agents, surfactants, flame retardants, 1 type or 2 types or more of ultraviolet absorbers, decolorizers, colorants, adhesion-imparting agents, etc.) may be contained, but the total content of the ND particles and the liquid crystal polymer in the total amount of nonvolatile content contained in the composition The amount is, for example, 10% by weight or more, preferably 20% by weight or more, more preferably 30% by weight or more, still more preferably 40% by weight or more, still more preferably 50% by weight or more, still more preferably 60% by weight or more, particularly preferably. Is 70% by weight or more.
  • the filler includes a fibrous, powdery, or plate-like inorganic or organic filler.
  • the fibrous filler examples include glass fiber, milled glass fiber, carbon fiber, asbestos fiber, silica fiber, silica-alumina fiber, alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, titanic acid.
  • Silica fiber such as potassium fiber, wollastonite, magnesium sulfate fiber, aluminum borate fiber, inorganic fibrous material such as metal (for example, stainless steel, aluminum, titanium, copper, brass, etc.); polyamide resin , High melting point organic fibrous materials such as fluororesin, polyester resin, and acrylic resin.
  • a particularly typical fibrous filler is glass fiber.
  • the particulate filler examples include metal oxides such as iron oxide, titanium oxide, zinc oxide, antimony trioxide, and alumina; metal carbonates such as calcium carbonate and magnesium carbonate; metals such as calcium sulfate and barium sulfate Sulfates of carbon black, graphite, silica, quartz powder, glass beads, glass balloons, glass powder, calcium oxalate, aluminum oxalate, kaolin, clay, diatomaceous earth, wollastonite, etc., ferrite, Examples thereof include silicon carbide, silicon nitride, boron nitride, and various metal powders.
  • metal oxides such as iron oxide, titanium oxide, zinc oxide, antimony trioxide, and alumina
  • metal carbonates such as calcium carbonate and magnesium carbonate
  • metals such as calcium sulfate and barium sulfate Sulfates of carbon black, graphite, silica, quartz powder, glass beads, glass balloons, glass powder, calcium ox
  • Examples of the plate-like filler include mica, glass flakes, talc, and various metal foils.
  • ND particles exhibit the effect of capturing peroxy radicals generated in the liquid crystal polymer. Since the composition of the present invention contains ND particles having the above-mentioned characteristics, an increase in radical generation amount (or peroxy radical generation amount) is suppressed by capturing peroxy radicals in ND particles even in a high temperature environment. In addition, the toughness of the liquid crystal polymer is reduced due to oxidative degradation due to the generated peroxy radicals, and embrittlement can be prevented, and yellowing due to oxidative degradation can be suppressed and the hue can be maintained well.
  • the radical generation amount at 25 ° C. of the composition of the present invention measured by electron spin resonance (ESR) is, for example, 2 ⁇ 10 16 to 2 ⁇ 10 18 spins / g, preferably 1 ⁇ 10 17 to 10 ⁇ . 10 17 spins / g, particularly preferably 2 ⁇ 10 17 to 5 ⁇ 10 17 spins / g.
  • the radical generation amount at 320 ° C. of the composition of the present invention measured by electron spin resonance (ESR) is, for example, 2 ⁇ 10 16 to 2 ⁇ 10 18 spins / g, preferably 5 ⁇ 10 16 to 10 ⁇ . 10 17 spins / g, particularly preferably 1 ⁇ 10 17 to 5 ⁇ 10 17 spins / g.
  • the radical generation amount at 400 ° C. of the composition of the present invention measured by electron spin resonance (ESR) is, for example, 2 ⁇ 10 16 to 2 ⁇ 10 18 spins / g, preferably 1 ⁇ 10 17 to 10 ⁇ . 10 17 spins / g, particularly preferably 2 ⁇ 10 17 to 10 ⁇ 10 17 spins / g.
  • the radical generation amount of the composition of the present invention exceeds the above range, it is difficult to prevent oxidative deterioration of the liquid crystal polymer due to peroxy radicals, so that it does not adversely affect melt moldability and polymer mechanical properties.
  • a peroxy radical scavenger may be added.
  • the radical generation amount is below the above range, the lifetime of the peroxy radical is short, and the oxidation reaction derived from oxygen becomes active, so that the physical properties of the obtained solidified product are deteriorated (for example, toughness is reduced and embrittled) Etc.).
  • the composition of the present invention exhibits the effect of capturing peroxy radicals generated in the liquid crystal polymer by the ND particles. Therefore, even when exposed to a high temperature environment, an increase in the amount of radicals that cause oxidative degradation of the liquid crystal polymer is suppressed.
  • the radical generation amount at 400 ° C. measured by electron spin resonance (ESR) is, for example, 3.0 times or less, preferably 2.5 times or less, particularly preferably 2.2 times the radical generation amount at 25 ° C. It is as follows. If the increase in the amount of radical generation exceeds the above range, the radical scavenging effect by the ND particles is insufficient (peroxy radical stabilization is insufficient), and the effect of preventing oxidative degradation of the liquid crystal polymer is difficult to obtain. Tend.
  • the composition of the present invention contains ND particles having an effect of scavenging peroxy radicals, it has excellent heat resistance, can be prevented from oxidative deterioration even when exposed to a high temperature environment, and has a temperature rising rate of 10 ° C./min.
  • the weight reduction rate when the temperature is raised from 50 ° C. to 370 ° C. (in air) is, for example, 2.5% by weight or less, preferably less than 2.0% by weight, particularly preferably 1.8% by weight or less. .
  • the composition of the present invention contains ND particles having excellent heat resistance and antioxidation effect together with the liquid crystal polymer, the composition is heated at a temperature at which the liquid crystal polymer contained in the composition melts.
  • the ND particles can exhibit an excellent antioxidant effect (or radical scavenging effect) without being decomposed, and exhibit the effect of scavenging radicals generated in the liquid crystal polymer. Thereby, the oxidative deterioration of the liquid crystal polymer due to radicals can be prevented, and yellowing of the liquid crystal polymer can be suppressed.
  • composition of the present invention can be used, for example, as a printed circuit board mounting component, a connector / bobbin / optical pickup component case, a micromotor component or other electric / electronic component material; a compressor component, a shock absorber component or other automotive component material. It can be preferably used.
  • the molded product of the present invention comprises a solidified product of the above composition.
  • the molded body of the present invention can be produced, for example, by filling the melt of the above composition into a mold having a concave portion having a reverse shape of a desired shape, and then cooling to solidify the above composition. it can.
  • the above composition is melted by heating at a temperature equal to or higher than the melting point or softening point of the liquid crystal polymer contained therein.
  • the composition is solidified by cooling to a temperature lower than the melting point or softening point of the liquid crystal polymer contained therein to form a solidified product.
  • the above composition can be molded by, for example, a melt molding method such as an injection molding method or an extrusion injection molding method.
  • the molded product thus obtained has a good hue and excellent appearance. Moreover, it is excellent in heat resistance, and it can suppress the fall of mechanical characteristics (toughness etc.) over a long period of time at the temperature lower than melting
  • the molded article of the present invention is suitable as, for example, printed circuit board mounting parts, connector / bobbin / optical pickup parts cases, electric / electronic parts such as micro motor parts, automobile parts such as compressor parts, shock absorber parts, etc. Can be used.
  • the antioxidant of the present invention is characterized by containing ND particles (preferably, the above-mentioned ND particles).
  • the antioxidant of the present invention can be suitably used as an antioxidant for thermoplastic resins.
  • the antioxidant of the present invention is excellent in heat resistance, and the 5% weight loss temperature measured at a heating rate of 10 ° C./min (in air) is, for example, 450 ° C. or higher (eg, 450 to 600 ° C.), preferably 500 ° C. That's it.
  • the 5% weight loss temperature can be measured by, for example, TG / DTA (simultaneous measurement of differential heat and thermogravimetry).
  • the antioxidant of the present invention is excellent in heat resistance, it has a high melting point (or softening temperature) of 250 ° C. or higher (eg 250 to 550 ° C.), preferably 300 ° C. or higher, particularly preferably 320 ° C. or higher. It can be used as an antioxidant for resins.
  • an antioxidant for a liquid crystal polymer (particularly preferably a liquid crystal polyester and / or a liquid crystal polyester amide) among thermoplastic resins. It can be suitably used as an agent.
  • the liquid crystal polymer undergoes oxidative degradation due to the decomposition of the ester bond or amide bond site by radicals.
  • the ND particles capture peroxy radicals, thereby allowing the ester bond and the liquid crystal polymer to bond with each other. This is because oxidative degradation of the amide bond site is suppressed and stabilized.
  • the antioxidant of the present invention may contain other components in addition to the ND particles, but the proportion of the ND particles in the total amount of the antioxidant is, for example, 60% by weight or more, preferably 70% by weight or more. Particularly preferably, it is 80% by weight or more, and most preferably 90% by weight or more. The upper limit is 100% by weight. When content of ND particle
  • Preparation Example 1 (Preparation of liquid crystal polymer (LCP1)) After the following raw materials were charged into the polymerization vessel, the temperature of the reaction system was raised to 140 ° C. and reacted at that temperature for 1 hour. Thereafter, the temperature is further raised to 325 ° C. over 3.5 hours, and then reduced to 5 Torr (ie, 667 Pa) over 20 minutes while distilling acetic acid, excess acetic anhydride, and other low-boiling components. Melt polymerization was performed.
  • LiCP1 liquid crystal polymer
  • the obtained liquid crystal polymer had a melting point of 280 ° C. and a melt viscosity at 300 ° C. of 44.0 Pa ⁇ s.
  • HBA 4-hydroxybenzoic acid
  • HNA 2-Hydroxy-6-naphthoic acid
  • Metal catalyst (potassium acetate catalyst); 165 mg Acylating agent (acetic anhydride); 1714 g
  • Preparation Example 2 (Preparation of liquid crystal polymer (LCP2)) After the following raw materials were charged into the polymerization vessel, the temperature of the reaction system was raised to 140 ° C. and reacted at that temperature for 1 hour. Thereafter, the temperature is further increased to 340 ° C. over 4.5 hours, and then the pressure is reduced to 10 Torr (ie, 1330 Pa) over 15 minutes, while acetic acid, excess acetic anhydride, and other low boiling points are distilled off. Melt polymerization was performed.
  • LCP2 liquid crystal polymer
  • the stirring torque reaches a predetermined value, nitrogen is introduced to change from the reduced pressure state to the normal pressure state, the liquid crystal polymer is discharged from the lower part of the polymerization vessel, the strand is pelletized, and the pellet-like liquid crystal polymer is removed. Obtained.
  • the obtained pellet-like liquid crystal polymer was further heat-treated at 300 ° C. for 2 hours under a nitrogen stream.
  • the obtained liquid crystal polymer had a melting point of 336 ° C. and a melt viscosity at 350 ° C. of 19.0 Pa ⁇ s.
  • HBA 4-hydroxybenzoic acid
  • HNA 2-hydroxy-6-naphthoic acid
  • TA Terephthalic acid
  • BP 4,4′-dihydroxybiphenyl
  • APAP 4-acetoxyaminophenol
  • 126 g 5 mol%) 110 mg of metal catalyst (potassium acetate catalyst)
  • Acylating agent acetic anhydride
  • Preparation Example 3 (Preparation of liquid crystal polymer (LCP3)) After the following raw materials were charged into the polymerization vessel, the temperature of the reaction system was raised to 140 ° C. and reacted at that temperature for 1 hour. Thereafter, the temperature is further raised to 360 ° C. over 5.5 hours, and then the pressure is reduced to 5 Torr (ie, 667 Pa) over 30 minutes, while acetic acid, excess acetic anhydride, and other low boiling points are distilled off. Melt polymerization was performed.
  • LCP3 liquid crystal polymer
  • the stirring torque reaches a predetermined value, nitrogen is introduced to change from the reduced pressure state to the normal pressure state, the liquid crystal polymer is discharged from the lower part of the polymerization vessel, the strand is pelletized, and the pellet-like liquid crystal polymer is removed. Obtained.
  • the obtained pellet-like liquid crystal polymer was further heat-treated at 300 ° C. for 8 hours under a nitrogen stream.
  • the obtained liquid crystal polymer had a melting point of 352 ° C. and a melt viscosity at 380 ° C. of 23.0 Pa ⁇ s.
  • HBA 4-hydroxybenzoic acid
  • HNA 2-hydroxy-6-naphthoic acid
  • TA Terephthalic acid
  • BP 4,4′-dihydroxybiphenyl
  • BP 4,4′-dihydroxybiphenyl
  • Metal catalyst potassium acetate catalyst
  • Acylating agent acetic anhydride
  • melt viscosity The melt viscosity of the liquid crystal polymer was measured in accordance with ISO11443 under the following conditions using an orifice having an inner diameter of 1 mm and a length of 20 mm using a capillograph (piston diameter: 10 mm) manufactured by Toyo Seiki Seisakusho. Cylinder temperature: When the liquid crystal polymer is LCP1: 300 ° C When the liquid crystal polymer is LCP2: 350 ° C. When the liquid crystal polymer is LCP3: 380 ° C. Shear rate: 1000 sec -1
  • Example 1 Synthesis of antioxidant (ND1)
  • a molded explosive with an electric detonator attached was placed inside a pressure-resistant container (made of iron, volume: 15 m 3 ) for detonation, and the container was sealed.
  • 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. After this cooling, the ND particle coarse product adhering to the inner wall of the container (including the ND particle aggregate and soot produced by the above detonation method) is scraped off with a spatula, The product was recovered.
  • the acid treatment was performed on the crude ND particle product obtained by performing the production process as described above a plurality of times. Specifically, a slurry obtained by adding 6 L of 10 wt% hydrochloric acid to 200 g of the ND particle crude product was heated at 85 to 100 ° C. for 1 hour under reflux under normal pressure conditions. It was. After cooling, the solid content (including ND particle aggregates and soot) was washed with water by decantation. The solid content was washed repeatedly with decantation until the pH of the precipitate reached 2 from the low pH side.
  • oxidation treatment was performed. Specifically, 12 L of 98% by weight sulfuric acid aqueous solution and 1 L of 97% by weight nitric acid aqueous solution were added to the precipitate obtained through decantation after acid treatment (including ND particle aggregates) to form a slurry. Thereafter, the slurry was subjected to a heat treatment at 140 to 160 ° C. for 48 hours under reflux under normal pressure conditions. After cooling, the solid content (including ND particle aggregates) was washed with water by decantation. The supernatant liquid at the beginning of water washing was colored, and the solid contents were washed repeatedly by decantation until the supernatant liquid became transparent visually.
  • the 5% weight loss temperature of the ND particle powder (ND1) measured by TG / DTA (simultaneous measurement of differential heat and thermogravimetry) measured at a heating rate of 10 ° C./min (in air) was 523 ° C. It was.
  • Example 2 Synthesis of antioxidant (ND2)
  • ND1 (4.5 g) obtained as described above is left in the core tube of the gas atmosphere furnace and nitrogen gas is continuously passed through the core tube at a flow rate of 1 L / min for 30 minutes.
  • the flow gas was switched from nitrogen to a mixed gas of oxygen and nitrogen (oxygen concentration: 4% by volume), and the mixed gas was continuously passed through the core tube at a flow rate of 1 L / min.
  • 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 ND particle powder in a furnace, maintaining the temperature conditions in a furnace at 400 degreeC.
  • the processing time was 3 hours.
  • ND particle powder (ND2) was obtained.
  • the ratio (yield) of the amount of the ND particle powder after the heating oxidation step to the amount of the ND particle powder before being subjected to the heating oxidation step was 96%.
  • FT-IR as shown in FIG. 2, an absorption peak derived from the ketone group (C ⁇ O) in the surface functional group was observed at 1776.44 cm ⁇ 1 . No noticeable absorption peak was observed at 2800 to 3000 cm ⁇ 1 .
  • Example 3 Synthesis of antioxidant (ND3)
  • An ND particle powder (ND3) was obtained in the same manner as in Example 2 except that the heating set temperature in the heating oxidation step was changed to 475 ° C.
  • the rate of temperature increase was 10 ° C./min from 455 ° C., which is 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 the ND particle powder after the heating oxidation step to the amount of the ND particle powder before being subjected to the heating oxidation step was 70%.
  • FT-IR as shown in FIG. 3, an absorption peak derived from a ketone group (C ⁇ O) in the surface functional group was observed in the vicinity of 1800 cm ⁇ 1 . No noticeable absorption peak was observed at 2800 to 3000 cm ⁇ 1 .
  • Example 4 Synthesis of antioxidant (ND4)
  • ND1 (4.5 g) obtained in the same manner as in Example 1 was left in the core tube of the gas atmosphere furnace, and nitrogen gas was continuously passed through the core tube at a flow rate of 1 L / min for 30 minutes.
  • the flowing gas was switched from nitrogen to a mixed gas of hydrogen and nitrogen, and the mixed gas was continuously passed through the core tube at a flow rate of 1 L / min.
  • the hydrogen concentration in the mixed gas is 2% by volume.
  • the temperature in the furnace was raised to a heating set temperature of 800 ° C.
  • the heating rate was 10 ° C./min from 780 ° C., which is 20 ° C.
  • ND particle powder (ND4) was obtained.
  • the ratio (yield) of the amount of the ND particle powder after the heat reduction treatment to the amount of the ND particle powder before being subjected to the heat reduction treatment was 93%.
  • FT-IR measurement> A Fourier transform infrared spectrophotometer (trade name “FT-720”, manufactured by HORIBA, Ltd.) and heated vacuum stirring reflection (trade name “Heat Chamber Type—1000 ° C.”, manufactured by ST Japan Co., Ltd.) ) was used to measure. In order to remove adsorbed water of ND particles, FT-IR measurement was performed after heating at 150 ° C. for 1 minute under a vacuum degree of 2 ⁇ 10 ⁇ 3 Pa.
  • Measuring device JES-FE3T (manufactured by JEOL Ltd.) Attached device: High temperature cavity (manufactured by JEOL Ltd.) Measurement conditions Measurement temperature: Room temperature to set temperature Central magnetic field: Near 3278G Magnetic field sweep range: 500G Modulation: 100kHz, 1G Microwave: 9.21 GHz, 1 mW Sweep time: 120s x 1time Time constant: 100 ms Number of data points: 4095 points Cavity: TE011, cylindrical type
  • the signal intensity of the localized spin is proportional to the inverse of absolute temperature (1 / T)
  • the signal intensity at each temperature is converted to the signal intensity at room temperature and compared with the signal intensity of the standard sample measured at room temperature. The number of unpaired electrons was calculated.
  • composition of the present invention suppresses an increase in the amount of radical generation due to heat and suppresses oxidative degradation of the liquid crystal polymer.
  • the obtained composition was molded under the following molding conditions using a molding machine (trade name “TR-100EH”, manufactured by Sodick Co., Ltd.) to obtain a molded body of 50 mm ⁇ 5 mm ⁇ 0.8 mm.
  • a molding machine trade name “TR-100EH”, manufactured by Sodick Co., Ltd.
  • the molded body before and after the heat aging test is subjected to a three-point bending test under the following test conditions using a Tensilon universal testing machine (trade name “RTC-1325A”, manufactured by Orientec Co., Ltd.).
  • the bending strain (%) until the molded body broke was calculated from the following formula (1), and the toughness retention was calculated from the following formula (2).
  • Breaking bending strain (%) 600 ⁇ [deflection (mm)] ⁇ [test specimen thickness (mm)] / [distance between fulcrums (mm)] (1)
  • Toughness retention (%) [Bending bending strain at 2000 hours of heat aging (%)] / [Bending bending strain at 0 hours of heat aging (%)] ⁇ 100 (2)
  • Test speed 1mm / min Distance between fulcrums: 12.8mm Indenter radius: 0.5 mm Support base radius: 2mm
  • the maximum peak of 1700 ⁇ 1850 cm -1 is greater than the maximum peak of 2800 ⁇ 3000cm -1, [1] ⁇ [9] The composition as described in any one of these.
  • a radical generation amount at 25 ° C. measured by an electron spin resonance method is 2 ⁇ 10 16 to 2 ⁇ 10 18 spins / g. object.
  • the radical generation amount at 400 ° C. measured by an electron spin resonance method is 3.0 times or less the radical generation amount at 25 ° C., according to any one of [1] to [12] Composition.
  • Any of [1] to [13], wherein the weight loss rate when heated from 50 ° C. to 370 ° C. at a temperature rising rate of 10 ° C./min in air is 2.5% by weight or less.
  • a molded article comprising a solidified product of the composition according to any one of [1] to [14].
  • An antioxidant for thermoplastic resin comprising nanodiamond particles.
  • thermoplastic resins as described in any one of these.
  • the antioxidant for thermoplastic resins according to any one of [16] to [20] which is an antioxidant for thermoplastic resins having a melting point or softening temperature of 250 ° C. or higher.
  • thermoplastic resin according to any one of [16] to [21], wherein a 5% weight loss temperature measured at a heating rate of 10 ° C./min (in air) is 450 ° C. or higher. Inhibitor.
  • the maximum peak of 1700 ⁇ 1850 cm -1 it is greater than the maximum peak of 2800 ⁇ 3000cm -1, [24] ⁇
  • thermoplastic resins according to any one of [24] to [28] wherein the nanodiamond particles are detonated nanodiamond particles.
  • the median diameter of the nanodiamond particles is 10 nm or less.
  • the nanodiamond particles are nanodiamond particles having a carbonyl group on the surface.
  • thermoplastic resins In the infrared absorption spectrum by Fourier transform infrared spectrophotometer of nanodiamond particles, the maximum peak of 1700 ⁇ 1850 cm -1 it is greater than the maximum peak of 2800 ⁇ 3000cm -1, [24] ⁇ [31] Use as an antioxidant for thermoplastic resins according to any one of the above. [33] A method for producing an antioxidant for thermoplastic resin, comprising producing an antioxidant for thermoplastic resin using nanodiamond particles.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

L'invention concerne une composition contenant un polymère à cristaux liquides et un antioxydant présentant une excellente résistance à la chaleur. Cette composition contient : au moins un type de polymère à cristaux liquides choisi parmi un polyester à cristaux liquides et un polyesteramide à cristaux liquides; et des nanoparticules de diamant en quantités grâce auxquelles la proportion des nanoparticules de diamant est comprise entre 0,001 et 5 parties en poids par rapport à 100 parties en poids du polymère à cristaux liquides. Le polymère à cristaux liquides a de préférence la constitution présentée ci-dessous. Par rapport à toutes les unités constitutives qui constituent le polymère à cristaux liquides, la teneur en unités constitutives représentées par la formule (I) est comprise entre 50 et 100 % en moles, la teneur en unités constitutives représentées par la formule (II) est comprise entre 0 et 25 % en moles, et la teneur en unités constitutives représentées par la formule (III) est comprise entre 0 et 25 % en moles.
PCT/JP2019/022585 2018-06-13 2019-06-06 Composition WO2019240013A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021033578A1 (fr) * 2019-08-22 2021-02-25 Ｅｎｅｏｓ株式会社 Particules de polymère à cristaux liquides, composition de résine polyester thermoplastique, et corps moulé

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004051937A (ja) * 2002-05-31 2004-02-19 Univ Nihon 高分子複合材料及びその製造方法
JP2005144628A (ja) * 2003-11-18 2005-06-09 Kazariichi:Kk 研磨材
JP2006057005A (ja) * 2004-08-20 2006-03-02 Sumitomo Chemical Co Ltd 高熱伝導性の樹脂成形体
JP2006274486A (ja) * 2005-03-29 2006-10-12 Teijin Ltd 芳香族ポリアミドコンポジットファイバー及びその製造方法
JP2008169265A (ja) * 2007-01-10 2008-07-24 Kaneka Corp 電気絶縁性高熱伝導性熱可塑性樹脂組成物及び高熱伝導性成形体
JP2008297401A (ja) * 2007-05-30 2008-12-11 Kaneka Corp 高熱伝導性熱可塑性樹脂組成物
WO2010050202A1 (fr) * 2008-10-30 2010-05-06 株式会社カネカ Résine thermoplastique et composition de résine thermoplastique de conductivité thermique élevée
JP2012025930A (ja) * 2010-06-25 2012-02-09 Vision Development Co Ltd ダイヤモンド微粒子及び／又はカーボンナノチューブを含有するポリエステル樹脂の製造方法
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
JP2017213539A (ja) * 2016-06-02 2017-12-07 株式会社ダイセル 硬化樹脂膜製造方法および硬化樹脂膜
WO2018079597A1 (fr) * 2016-10-28 2018-05-03 株式会社ダイセル Additif destiné à des résines, et composition de résine

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7084133B2 (ja) 2017-12-26 2022-06-14 ポリプラスチックス株式会社 液晶性樹脂の製造方法
JP7083636B2 (ja) 2017-12-26 2022-06-13 ポリプラスチックス株式会社 液晶性樹脂の製造方法

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004051937A (ja) * 2002-05-31 2004-02-19 Univ Nihon 高分子複合材料及びその製造方法
JP2005144628A (ja) * 2003-11-18 2005-06-09 Kazariichi:Kk 研磨材
JP2006057005A (ja) * 2004-08-20 2006-03-02 Sumitomo Chemical Co Ltd 高熱伝導性の樹脂成形体
JP2006274486A (ja) * 2005-03-29 2006-10-12 Teijin Ltd 芳香族ポリアミドコンポジットファイバー及びその製造方法
JP2008169265A (ja) * 2007-01-10 2008-07-24 Kaneka Corp 電気絶縁性高熱伝導性熱可塑性樹脂組成物及び高熱伝導性成形体
JP2008297401A (ja) * 2007-05-30 2008-12-11 Kaneka Corp 高熱伝導性熱可塑性樹脂組成物
WO2010050202A1 (fr) * 2008-10-30 2010-05-06 株式会社カネカ Résine thermoplastique et composition de résine thermoplastique de conductivité thermique élevée
JP2012025930A (ja) * 2010-06-25 2012-02-09 Vision Development Co Ltd ダイヤモンド微粒子及び／又はカーボンナノチューブを含有するポリエステル樹脂の製造方法
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
JP2017213539A (ja) * 2016-06-02 2017-12-07 株式会社ダイセル 硬化樹脂膜製造方法および硬化樹脂膜
WO2018079597A1 (fr) * 2016-10-28 2018-05-03 株式会社ダイセル Additif destiné à des résines, et composition de résine

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021033578A1 (fr) * 2019-08-22 2021-02-25 Ｅｎｅｏｓ株式会社 Particules de polymère à cristaux liquides, composition de résine polyester thermoplastique, et corps moulé
US11999820B2 (en) 2019-08-22 2024-06-04 Eneos Corporation Liquid crystal polymer particles, thermosetting resin composition, and molded article

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