WO2022137998A1 - Composition de résine de polyacétal et article en contact avec un combustible - Google Patents

Composition de résine de polyacétal et article en contact avec un combustible Download PDF

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WO2022137998A1
WO2022137998A1 PCT/JP2021/043638 JP2021043638W WO2022137998A1 WO 2022137998 A1 WO2022137998 A1 WO 2022137998A1 JP 2021043638 W JP2021043638 W JP 2021043638W WO 2022137998 A1 WO2022137998 A1 WO 2022137998A1
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carbon
mass
resin composition
polyacetal resin
parts
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PCT/JP2021/043638
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English (en)
Japanese (ja)
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裕基 神田
智宏 門間
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ポリプラスチックス株式会社
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Priority to JP2022517896A priority Critical patent/JP7217385B2/ja
Priority to CN202180086478.9A priority patent/CN116783245A/zh
Publication of WO2022137998A1 publication Critical patent/WO2022137998A1/fr

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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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L59/00—Compositions of polyacetals; Compositions of derivatives of polyacetals
    • 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
    • C08L71/02—Polyalkylene oxides

Definitions

  • the present invention relates to a polyacetal resin composition and a fuel contact body formed by molding the polyacetal resin composition.
  • polyacetal resin (hereinafter, also referred to as "POM resin”) has excellent chemical resistance
  • molded products made from POM resin are widely used as automobile parts.
  • POM resin is used as a large component such as a fuel transfer unit represented by a fuel pump module or the like that comes into direct contact with fuel oil.
  • an injection-molded product manufactured from POM resin has residual stress inside the molded product due to cooling during injection molding.
  • cracks may occur at locations where the residual stress is large, which may cause troubles such as fuel leakage. Therefore, for countries where high-sulfur fuels are distributed, it is necessary to use a resin material having high resistance to high-sulfur fuels as a raw material.
  • the toughness is significantly increased. There is a problem that it decreases to. That is, in the POM resin composition, if the antistatic effect and the durability against the acid component are simultaneously realized, the toughness will be significantly reduced.
  • the present invention has been made in view of the above-mentioned conventional problems, and the problem is that the POM resin composition and fuel contact are endowed with durability and antistatic effect against high sulfur fuel without significantly reducing toughness. To provide the body.
  • One aspect of the present invention that solves the above problems is as follows. (1) (A) Polyacetal resin with 100 parts by mass, (B) Add 0.1 to 1.0 parts by mass of the antioxidant. (C) At least one of magnesium oxide and zinc oxide is added in an amount of 0.3 to 2.0 parts by mass. (D) Add 0.5 to 3.0 parts by mass of polyalkylene glycol. (E) 0.01 to 1.0 parts by mass of fatty acid ester of polyhydric alcohol having an esterification rate of 80% or more.
  • (F) Contains 0.3 to 2.5 parts by mass of a carbon-based conductive additive,
  • One of the (F) carbon-based conductive additives selected from only (F1) carbon nanostructures and a combination of (F1) carbon nanostructures and (F2) carbon black having a BET specific surface area of 300 m 2 / g or more. Is a polyacetal resin composition.
  • the polyacetal resin is a copolymer having a cyclic oligomer of formaldehyde as a main monomer and a compound selected from a cyclic ether having at least one carbon-carbon bond and / or a cyclic formal as a comonomer.
  • a fuel contact body comprising a molded product of the polyacetal resin composition according to any one of (1) to (5) above.
  • the POM resin composition of the present embodiment contains (A) 100 parts by mass of a polyacetal resin, (B) 0.1 to 1.0 parts by mass of an antioxidant, and (C) magnesium oxide and zinc oxide. At least one of polyhydric alcohols having an esterification rate of 0.3 to 2.0 parts by mass, (D) polyalkylene glycol of 0.5 to 3.0 parts by mass, and (E) esterification rate of 80% or more. It contains 0.01 to 1.0 part by mass of the fatty acid ester and 0.3 to 2.5 parts by mass of the (F) carbon-based conductive additive.
  • the (F) carbon-based conductive additive is selected from only (F1) carbon nanostructures and a combination of (F1) carbon nanostructures and (F2) carbon black having a BET specific surface area of 300 m 2 / g or more. It is characterized by being one.
  • durability against high sulfur fuel can be imparted by blending at least one of (C) magnesium oxide and zinc oxide with the POM resin.
  • (F) a carbon-based conductive additive conductivity can be imparted and an antistatic effect can be exhibited.
  • carbon black or the like is added in order to exhibit the antistatic effect, it causes a significant decrease in toughness in combination with magnesium oxide or the like.
  • the (F) carbon-based conductive additive imparts conductivity, a significant decrease in toughness can be suppressed.
  • the "high sulfur fuel” means a fuel having a sulfur component concentration of 0.1% by mass or more.
  • the (A) POM resin used in the present embodiment refers to a polymer compound having an oxymethylene group (-CH 2O- ) as a main constituent unit, and is a polyacetal polymer consisting substantially only of a repeating unit of an oximethylene group. , Polyacetal copolymer containing a small amount of other structural units in addition to the oxymethylene group and the like. Although any of these can be used, it is preferable to use a polyacetal copolymer as a substrate resin from the viewpoint of fuel resistance.
  • the polyacetal copolymer is preferably a polyacetal copolymer obtained by copolymerizing 0.5 to 30% by mass of a comonomer component, and particularly preferably 0.5 to 10% by mass of a comonomer component. It is made by polymerizing.
  • the polyacetal copolymer obtained by copolymerizing a comonomer component is excellent in acid resistance and can maintain excellent thermal stability, mechanical strength and the like. Further, the polyacetal copolymer may have a branched structure or a crosslinked structure as well as a molecule having a linear structure.
  • a cyclic oligomer of formaldehyde typified by trioxane is used as the main monomer.
  • a compound selected from a cyclic ether having at least one carbon-carbon bond and / or a cyclic formal is used as the comonomer component.
  • examples of such comonomer include ethylene oxide, 1,3-dioxolane, diethylene glycol formal, 1,4-butanediol formal, 1,3-dioxane, propylene oxide and the like.
  • melt mass flow rate (MFR) measured at a measurement temperature of 190 ° C. and a load of 2.16 kg is 1 to 100 g / 10 minutes according to ISO1133. Particularly preferably, it is 5 to 30 g / 10 minutes.
  • Examples of the (B) antioxidant used in the present embodiment include aromatic amine-based antioxidants, hindered phenol-based antioxidants, and the like.
  • Examples of the aromatic amine-based antioxidant include N-phenyl-1-naphthylamine, bis (4-octylphenyl) amine, 4,4'-bis ( ⁇ , ⁇ -dimethylbenzyl) diphenylamine, and p- (p-toluenesulfonyl).
  • Diphenylamine N, N'-di-2-naphthyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, N-phenyl-N'-(1,3-dimethylbutyl)- Examples thereof include p-phenylenediamine, N-phenyl-N'-(3-methacryloyloxy-2-hydroxypropyl) -p-phenylenediamine and the like. Of these, 4,4'-bis ( ⁇ , ⁇ -dimethylbenzyl) diphenylamine is preferable.
  • hindered phenolic antioxidants examples include 2,2'-methylenebis (4-methyl-6-t-butylphenol) and hexamethylene-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl).
  • Propionate Tetrakiss [Methyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] Methyl, Triethyleneglycol-bis [3- (3-t-butyl-4-hydroxy-5) -Methylphenyl) propionate], 1,3,5-trimethyl-2,4,6-tris (3', 5'-di-t-butyl-4-hydroxy-benzyl) benzene, n-octadecyl-3- ( 4'-hydroxy-3', 5'-di-t-butylphenyl) propionate, 4,4'-methylenebis (2,6-di-t-butylphenol), 4,4'-butylidenebis (6-
  • At least one or two or more selected from these antioxidants can be used.
  • the blending amount of the (B) antioxidant in the present embodiment is 0.1 to 1.0 part by mass and 0.2 to 0.8 part by mass with respect to 100 parts by mass of the (A) POM resin. Is more preferable.
  • the POM resin composition of the present embodiment contains at least one of magnesium oxide and zinc oxide (hereinafter, also referred to as “component (C)”).
  • component (C) used in the present embodiment is a balance between improvement of high sulfur resistance fuel (durability against high sulfur fuel (hereinafter, also referred to as “fuel resistance”)) and performance such as mechanical properties and moldability. Is excellent and preferable.
  • the BET specific surface area is 100 m 2 / g or more and the average particle size is 1.5 ⁇ m or less.
  • the BET specific surface area of magnesium oxide is preferably 100 to 500 m 2 / g, more preferably 120 to 300 m 2 / g.
  • the average particle size of magnesium oxide is preferably 0.2 to 1.3 ⁇ m, more preferably 0.3 to 1.0 ⁇ m.
  • the average particle size is determined by the particle size of 50% of the integrated value in the particle size distribution (volume basis) measured by the laser diffraction / scattering method.
  • the blending amount of the component (C) in the present embodiment is 0.3 to 2.0 parts by mass and 1.0 to 1.8 parts by mass with respect to 100 parts by mass of the (A) POM resin. preferable.
  • the amount of the component (C) is 0.3 parts by mass or more, it is particularly excellent in fuel resistance, and stable production is possible when it is 2.0 parts by mass or less, and the machine is within 1.8 parts by mass. Especially excellent in the balance of characteristics.
  • the amount of the component (C) increased, the decomposition of unstable terminals in the POM resin was sometimes promoted, but the (A) POM resin of the present embodiment can suppress the decomposition.
  • (C) It was possible to find the characteristic of improving fuel resistance by increasing the amount of the component.
  • (D) Polyalkylene Glycol The type of (D) polyalkylene glycol used in the present embodiment is not particularly limited, but from the viewpoint of affinity with the POM resin, those containing polyethylene glycol and / or polypropylene glycol are preferable, and polyethylene glycol is contained. The one is more preferable.
  • the number average molecular weight (Mn) of the polyalkylene glycol is not particularly limited, but is preferably 1,000 or more and 50,000 or less, and 5,000 or more and 30,000 or less, from the viewpoint of dispersibility in the POM resin. It is more preferable to have.
  • the number average molecular weight is assumed to be a polystyrene-equivalent molecular weight determined by size exclusion chromatography (SEC) using tetrahydrofuran (THF) as a solvent.
  • the content of (D) polyalkylene glycol in the present embodiment is 0.5 to 3.0 parts by mass and 1.0 to 2.0 parts by mass with respect to 100 parts by mass of (A) POM resin. Is more preferable. If the amount of (D) polyalkylene glycol is small, sufficient stress relaxation may not be performed. If the amount of (D) polyalkylene glycol is excessive, the mechanical properties of the molded product may deteriorate.
  • the fatty acid ester of the (E) polyhydric alcohol used in the present embodiment has an esterification rate of 80% or more. If the esterification rate is less than 80%, the fuel resistance is poor.
  • the esterification rate of the fatty acid ester of the polyhydric alcohol is preferably 85% or more.
  • the polyhydric alcohol may be aliphatic or aromatic, but (A) it is preferably aliphatic in terms of affinity with the POM resin.
  • the valence of the polyhydric alcohol is not particularly limited, but it is preferably 3 or more and 4 or less.
  • the number of carbon atoms of the polyhydric alcohol is not particularly limited, but is preferably 3 or more and 10 or less, and preferably 3 or more and 5 or less, in terms of affinity with the (A) POM resin. More preferred.
  • Preferred polyhydric alcohols for forming the ester of the component (E) include, for example, glycerin, trimethylolpropane, pentaerythritol, mesoerythritol, pentitos, hexitol, sorbitol and the like, and POM after immersion in sulfur fuel.
  • the polyhydric alcohol is preferably pentaerythritol in that the mass loss of the resin composition can be suppressed to a low level.
  • the type of fatty acid is not particularly limited, but (A) a fatty acid having 10 or more and 30 or less carbon atoms is preferable, and an aliphatic having 10 or more and 20 or less carbon atoms is preferable in terms of compatibility with (A) POM resin. It is more preferably a carboxylic acid.
  • Preferred fatty acids for forming the ester of the component (E) include, for example, stearic acid, palmitic acid, lauric acid and the like, and preferably stearic acid.
  • the component (E) is preferably an ester compound of a polyhydric alcohol having 3 or more carbon atoms and a fatty acid. Specifically, glycerin tristearate and pentaerythritol tetrastearate are preferably used, and pentaerythritol tetrastearate is more preferably used. As the component (E), two or more kinds of esterified products having different polyhydric alcohols and fatty acids and esterified products having different esterification rates may be used in combination.
  • the content of the fatty acid ester of (E) polyhydric alcohol in the present embodiment is 0.01 to 1.0 part by mass and 0.05 to 1.0 part by mass with respect to 100 parts by mass of (A) POM resin. Is more preferable.
  • (F) Carbon-based conductive additive In the POM resin composition of the present embodiment, a predetermined amount of (F) carbon-based conductive additive is blended with respect to (A) POM resin.
  • the (F) carbon-based conductive additive is only (F1) carbon nanostructure (hereinafter, also referred to as “CNS”), and (F1) carbon nanostructure and (F2) carbon having a BET specific surface area of 300 m 2 / g or more. It is one selected from the combination with black. Then, by adding the (F) carbon-based conductive additive to the POM resin composition, conductivity is imparted and an antistatic effect is exhibited.
  • the CNS used in the present embodiment is a structure containing a plurality of carbon nanotubes in a bonded state, and the carbon nanotubes are bonded to other carbon nanotubes by a branched bond or a crosslinked structure. Details of such CNS are described in US Patent Application Publication No. 2013-0071565, US Pat. No. 9,113,031, US Pat. No. 9,447,259, US Pat. No. 9,111,658. It is described in the specification.
  • FIG. 1 schematically shows the CNS used in the present embodiment
  • (A) is a state before melt-kneading with POM resin
  • (B) is a state immediately after the start of melt-kneading
  • (C) is after melt-kneading. Indicates the state of.
  • the CNS 10 before melt-kneading forms a structure in which a large number of branched carbon nanotubes 12 are entangled and bonded.
  • the CNS 10 is poured into the POM resin 20 and melt-kneaded, the CNS 10 is divided into a large number as shown in FIG. 1 (B).
  • each of the carbon nanotubes 12 is in contact with each other via the contact point 14. That is, in the state of FIG. 1C, in the POM resin, a large number of carbon nanotubes 12 are in contact with each other over a wide range to form a conductive path, so that conductivity is exhibited. Further, it is considered that the carbon nanotubes 12 are randomly entangled to form a three-dimensional network structure, so that the decrease in toughness can be suppressed.
  • the CNS shown in FIG. 1 (A) has a predetermined flake shape.
  • the flake-shaped CNS shown in FIG. 1 (A) contains a plurality of carbon nanotubes, and the carbon nanotubes are branched, crosslinked, and share a common wall with each other.
  • not all of the carbon nanotubes have structural characteristics such as branching, cross-linking, and sharing a common wall, and the carbon nanotubes as a whole have at least one of these structural characteristics. It suffices to have.
  • the form shown in FIG. 1 (C) is obtained by melt-kneading.
  • the flake-shaped CNS as described above is obtained by growing the CNS on a growth substrate such as a fiber material and taking out the CNS from the growth substrate.
  • Growth substrates such as fibers, tow, yarn, woven fabrics, non-woven fabrics, sheets, tapes and belts can be used in the CNS growth process. That is, the growth base material can be a fiber material having a size that can be spooled, and the CNS can be continuously formed while the growth base material is conveyed. More specifically, the catalyst can be applied to the growth substrate and the CNS can be grown by the pore CVD process. Then, the growth substrate on which the CNS is formed can be stored and then wound up for taking out the CNS.
  • a catalyst containing a plurality of transition metal nanoparticles When growing CNS on a growth substrate, it is preferable to use a catalyst containing a plurality of transition metal nanoparticles.
  • the catalyst can be applied onto the growth substrate via particle adsorption, for example, direct catalyst application using vapor deposition with a liquid or colloidal precursor.
  • Transition metal nanoparticle catalysts include d-block transition metals or d-block transition metal salts.
  • the transition metal salt may be applied to the growth substrate without heat treatment, or the transition metal salt may be converted to a zero-valent transition metal on the growth substrate by heat treatment.
  • CNS contains carbon nanotubes in a network having a complex structural morphology, which is a CNS on a growth substrate under the growth conditions of carbon nanotubes produced at a rapid growth rate of several microns per second. It is considered that it is derived from the formation of.
  • the CNS that grows on the fiber can be formed by techniques such as microcavities, heat and plasma enhanced CVD techniques, laser ablation, arc discharge, and high pressure carbon monoxide (HiPCO). It is also possible to ionize the acetylene gas to generate a low temperature carbon plasma for synthesizing carbon nanotubes. At this time, the plasma is directed at the fiber material having a catalyst.
  • the carbon nanotubes are formed by the size of the carbon nanotube forming catalyst. Further, the synthesis of CNS can be facilitated by heating the sized fiber material to about 550 to 800 ° C.
  • a process gas such as argon, helium, or nitrogen
  • a carbon-containing gas such as acetylene, ethylene, ethanol, or methane. Then, the carbon nanotube grows at the position of the carbon nanotube forming catalyst.
  • the CNS used in this embodiment may be a commercially available product.
  • ATHLOS 200, ATHLOS 100, etc. manufactured by CABOT can be used.
  • carbon black having a BET specific surface area of 300 m 2 / g or more is used among the carbon blacks.
  • the carbon black is not used alone, but in combination with CNS. Since the POM resin composition containing the carbon black has high conductivity, the conductivity can be maintained even when used in combination with CNS. On the contrary, the POM resin composition containing carbon black having a BET specific surface area of less than 300 m 2 / g has low conductivity, and it is necessary to increase the blending amount in order to sufficiently secure the conductivity, so that the toughness is increased. The decline cannot be suppressed.
  • the BET specific surface area is preferably 310 m 2 / g or more, more preferably 350 m 2 / g or more, and the upper limit is not particularly limited, but is about 2000 m 2 / g.
  • the BET specific surface area can be measured according to ASTM D4820.
  • Specific carbon blacks as described above include Ketjen Black EC300J (BET specific surface area: 800 m 2 / g), Ketjen Black EC600JD (BET specific surface area: 1270 m 2 / g), Lionite EC200L manufactured by Lion Co., Ltd. (BET specific surface area: 377 m 2 / g) and the like.
  • the (F) carbon-based conductive additive is blended with respect to 100 parts by mass of the POM resin.
  • the blending amount of the CNS is preferably 0.5 to 2.0 parts by mass, more preferably 0.6 to 1.8 parts by mass, still more preferably 0.8 to 1.5 parts by mass.
  • the mass ratio ((F2) / (F1)) of (F1) CNS and (F2) carbon black is preferably 10 or less. , It is more preferable that it is more than 0 and 5 or less. When the mass ratio is 10 or less, the balance between conductivity and toughness can be ensured. Further, the closer the value of F2 / F1 is to 0, the more the CNS is over-blended, but the CNS may be over-blended as such. However, considering that the CNS is expensive, the lower limit of the value of F2 / F1 is preferably 0.1 from the viewpoint of cost effectiveness.
  • the POM resin composition of the present embodiment may contain other components, if necessary.
  • One or more known stabilizers for the POM resin composition can be added as long as the purpose and effect of the POM resin composition of the present embodiment are not impaired.
  • the method for producing a molded product using the POM resin composition of the present embodiment is not particularly limited, and a known method can be adopted.
  • the POM resin composition of the present embodiment may be put into an extruder, melt-kneaded and pelletized, and the pellets may be put into an injection molding machine equipped with a predetermined mold and injection-molded. can.
  • the above-mentioned POM resin composition of the present embodiment can be used as an automobile part described later, or can be a molded product having an antistatic function and resistance to fuel.
  • the fuel contact body of the present embodiment includes a molded product of the above POM resin composition.
  • the molded product is obtained by molding using the above POM resin composition by a conventional molding method, for example, injection molding, extrusion molding, compression molding, blow molding, vacuum molding, foam molding, rotary molding or the like. be able to.
  • the fuel contact body of the present embodiment is not limited to the high sulfur fuel, but may be contacted with a low sulfur fuel.
  • each raw material component shown in Tables 1 to 4 was dry-blended, then put into a twin-screw extruder having a cylinder temperature of 200 ° C., melt-kneaded, and pelletized.
  • Tables 1 to 4 the numerical values of each component indicate parts by mass. The details of each raw material component used are shown below.
  • POM resin Polyacetal resin
  • A-1 A polyacetal copolymer obtained by copolymerizing 96.7% by mass of trioxane and 3.3% by mass of 1,3-dioxolane.
  • MFR measured at 190 ° C. with a load of 2160 g according to ISO1133): 9 g / 10 min
  • B-1 Tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] Methane (BASF, Irganox 1010)
  • B-2 4,4'-bis ( ⁇ , ⁇ -dimethylbenzyl) diphenylamine (manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd., Nocrack CD)
  • C Magnesium oxide, etc.
  • C-1 Magnesium oxide, BET specific surface area 135 m 2 / g, average particle size 0.9 ⁇ m (Kyowa Chemical Industry Co., Ltd., Kyowa Mag MF150)
  • C-2 Magnesium oxide, BET specific surface area 30 m 2 / g, average particle size 0.6 ⁇ m (Kyowa Chemical Industry Co., Ltd., Kyowa Mag MF30)
  • C-3 Magnesium oxide, BET specific surface area 155 m 2 / g, average particle size 7 ⁇ m (Kyowa Chemical Industry Co., Ltd., Kyowa Mag 150)
  • C-4 Zinc oxide (BET specific surface area 60-90 m 2 / g) (manufactured by Shodo Chemical Industry Co., Ltd., active zinc white AZO)
  • Polyalkylene Glycol D-1 Polyethylene Glycol (manufactured by Sanyo Chemical Industries, Ltd., PEG6000S)
  • E Fatty acid ester of polyhydric alcohol
  • E-1 Pentaerythritol tetrastearate (fatty acid ester of polyhydric alcohol with esterification rate of 80% or more, manufactured by Nichiyu Co., Ltd., Unistar H476)
  • E-2 Glycerin tristearate (fatty acid ester of polyhydric alcohol with esterification rate of 80% or more, manufactured by Riken Vitamin Co., Ltd., Poem S-95)
  • E-3 Glycerin monostearate (fatty acid ester of polyhydric alcohol with esterification rate of less than 80%, manufactured by Riken Vitamin Co., Ltd., Rikemar S-100A)
  • F Carbon Nanostructure, Carbon Black
  • F-1 Carbon Nanostructure (manufactured by CABOT, ATHLOS 200)
  • F-2 Carbon black (manufactured by Lion Corporation, Ketjen Black EC300J, BET specific surface area: 800 m 2 / g)
  • F-3 Carbon black (manufactured by Lion Corporation, Lionite EC200L, BET specific surface area: 377m 2 / g)
  • F-4 Carbon black (manufactured by Denka Co., Ltd., Denka black, BET specific surface area: 65 m 2 / g)
  • the multipurpose test piece described in ISO294-1 was subjected to an injection molding machine (EC40, manufactured by Toshiba Machine Co., Ltd.) under the conditions according to ISO9988-1 and ISO9988-1. ) was produced by injection molding and used for the evaluation of (2) and (3) below.
  • FIG. 2 (A) shows the front surface
  • FIG. 2 (B) shows the back surface
  • a conductive paint Dotite D500, manufactured by Fujikura Kasei Co., Ltd.
  • a predetermined region hatchched region in FIG. 2 on each surface of the test piece and dried.
  • DIGITAL MULTIMETER R6450 manufactured by Advantest
  • Comparative Example 1 is different from Example 2 in that the components (C) to (F) are not blended, and is inferior in fuel resistance and conductivity. Comparative Example 2 is inferior in conductivity to Example 2 in that the component (F) is not blended. Comparative Example 3 is different from Example 2 in that the component (C) is not blended, and is inferior in fuel resistance. Comparative Example 4 is different from Example 2 in that the component (D) is not blended, and is inferior in fuel resistance. Comparative Example 5 is different from Example 2 in that the component (C) is too small, and is inferior in fuel resistance.
  • Comparative Example 6 is inferior in toughness to Example 2 in that the component (C) is excessive and the component (F) is slightly increased.
  • Comparative Example 7 is different from Example 2 in that the component (D) is too small, and is inferior in fuel resistance.
  • Comparative Example 8 is inferior in toughness to Example 2 in that the component (D) is excessive and the component (F) is slightly increased.
  • Comparative Example 9 is inferior in fuel resistance to Example 2 in that the component (E) is excessive.
  • Comparative Example 10 is different from Example 2 in that an esterification rate of less than 80% is used as the component (E), and the fuel resistance is inferior.
  • Comparative Examples 11 and 12 are different from Example 2 in whether the component (F) is too small or excessive, respectively, Comparative Example 11 is inferior in conductivity, and Comparative Example 12 is inferior in toughness.
  • Comparative Example 13 is different from Example 20 in that the component (F) used in the combination of carbon nanostructure and carbon black is excessive, and is inferior in toughness.
  • Comparative Example 14 is different from Example 18 in that carbon black having an excessively small BET specific surface area is used, and is inferior in conductivity. From the above, it can be seen that good results cannot be obtained in all of the toughness, fuel resistance, and antistatic effect unless the components (A) to (F) are blended in a predetermined content.

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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne une composition de résine de polyacétal qui comprend 100 parties en masse d'une résine de polyacétal (A), 0,1 à 1,0 partie en masse d'un antioxydant (B), 0,3 à 2,0 parties en masse d'au moins l'un parmi l'oxyde de magnésium et l'oxyde de zinc (C), 0,5 à 3,0 parties en masse d'un polyalkylène glycol (D), 0,01 à 1,0 partie en masse d'un ester d'acide gras (E) d'un alcool polyhydrique, qui a un rapport d'estérification d'au moins 80 %, et de 0,3 à 2,5 parties en masse d'un additif électroconducteur à base de carbone (F). L'additif électroconducteur à base de carbone (F) est l'un choisi parmi une nanostructure de carbone (F1) seule et la combinaison d'une nanostructure de carbone (F1) avec un noir de carbone (F2) ayant une surface spécifique BET d'au moins 300 m2/g.
PCT/JP2021/043638 2020-12-23 2021-11-29 Composition de résine de polyacétal et article en contact avec un combustible WO2022137998A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2022075107A1 (fr) * 2020-10-09 2022-04-14

Citations (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007032081A1 (fr) * 2005-09-16 2007-03-22 Asahi Kasei Chemicals Corporation Melange maitre et composition contenant ledit melange maitre
JP2007084604A (ja) * 2005-09-20 2007-04-05 Asahi Kasei Chemicals Corp ポリオキシメチレン樹脂製ハードディスクランプ
JP2008527128A (ja) * 2005-01-14 2008-07-24 ビーエーエスエフ ソシエタス・ヨーロピア 導電性ポリオキシメチレン組成物
JP2008189891A (ja) * 2007-02-08 2008-08-21 Misuzu Kogyo:Kk ポリアセタール樹脂コンポジット材、ポリアセタール樹脂コンポジット材からなる平面カム、及びその平面カムの製造方法
JP2010144112A (ja) * 2008-12-22 2010-07-01 Polyplastics Co 燃料用部品
JP2011132370A (ja) * 2009-12-24 2011-07-07 Polyplastics Co ポリアセタール樹脂組成物の製造方法
JP2012140482A (ja) * 2010-12-28 2012-07-26 Hodogaya Chem Co Ltd ポリアセタール樹脂／カーボンナノチューブ導電性樹脂複合材料
CN102634162A (zh) * 2012-05-09 2012-08-15 四川大学 一种导热聚甲醛复合材料及其制备方法
CN102675818A (zh) * 2012-05-24 2012-09-19 兖矿鲁南化肥厂 一种增强增韧聚甲醛及其制备方法
JP2013028737A (ja) * 2011-07-29 2013-02-07 Showa Denko Kk ポリオキシメチレン樹脂組成物及びそれからなる成形品
CN103897331A (zh) * 2014-04-21 2014-07-02 四川大学 一种导热聚甲醛复合材料及其制备方法
JP2014122264A (ja) * 2012-12-20 2014-07-03 Asahi Kasei Chemicals Corp 導電性ポリアセタール樹脂組成物のペレット及びその製造方法
US20150318072A1 (en) * 2012-12-28 2015-11-05 Korea Engineering Plastics Co., Ltd. Carbon nanotube-polyoxymethylene resin composition having excellent electrical conductivity and improved processability and heat stability, and molded article formed therefrom
JP2015209474A (ja) * 2014-04-25 2015-11-24 ポリプラスチックス株式会社 ポリアセタール樹脂組成物、及びこのポリアセタール樹脂組成物の成形品を備える硫黄燃料接触体
JP2016020453A (ja) * 2014-07-15 2016-02-04 阪本薬品工業株式会社 ポリグリセリン系樹脂可塑剤、及びそれを含有するセラミックスラリー組成物、並びにセラミック成形体
JP2018172456A (ja) * 2017-03-31 2018-11-08 ポリプラスチックス株式会社 ポリアセタール樹脂組成物
JP2019218442A (ja) * 2018-06-19 2019-12-26 ポリプラスチックス株式会社 ポリアセタール樹脂組成物
WO2022004236A1 (fr) * 2020-06-30 2022-01-06 ポリプラスチックス株式会社 Composition de résine thermoplastique, élément associé ainsi que procédé de fabrication de celui-ci, et procédé de développement de conductivité pour composition de résine thermoplastique
WO2022004235A1 (fr) * 2020-06-30 2022-01-06 ポリプラスチックス株式会社 Composition de résine thermoplastique, élément associé ainsi que procédé de fabrication de celui-ci, et procédé de développement de conductivité pour composition de résine thermoplastique
WO2022009616A1 (fr) * 2020-07-10 2022-01-13 ポリプラスチックス株式会社 Composition de résine thermoplastique, élément, et procédé de fabrication et procédé d'amélioration de résistance mécanique pour élément formé à partir d'une composition de résine thermoplastique

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102587117B1 (ko) 2020-10-09 2023-10-10 포리프라스틱 가부시키가이샤 폴리아세탈 수지 조성물 및 자동차 부품

Patent Citations (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008527128A (ja) * 2005-01-14 2008-07-24 ビーエーエスエフ ソシエタス・ヨーロピア 導電性ポリオキシメチレン組成物
WO2007032081A1 (fr) * 2005-09-16 2007-03-22 Asahi Kasei Chemicals Corporation Melange maitre et composition contenant ledit melange maitre
JP2007084604A (ja) * 2005-09-20 2007-04-05 Asahi Kasei Chemicals Corp ポリオキシメチレン樹脂製ハードディスクランプ
JP2008189891A (ja) * 2007-02-08 2008-08-21 Misuzu Kogyo:Kk ポリアセタール樹脂コンポジット材、ポリアセタール樹脂コンポジット材からなる平面カム、及びその平面カムの製造方法
JP2010144112A (ja) * 2008-12-22 2010-07-01 Polyplastics Co 燃料用部品
JP2011132370A (ja) * 2009-12-24 2011-07-07 Polyplastics Co ポリアセタール樹脂組成物の製造方法
JP2012140482A (ja) * 2010-12-28 2012-07-26 Hodogaya Chem Co Ltd ポリアセタール樹脂／カーボンナノチューブ導電性樹脂複合材料
JP2013028737A (ja) * 2011-07-29 2013-02-07 Showa Denko Kk ポリオキシメチレン樹脂組成物及びそれからなる成形品
CN102634162A (zh) * 2012-05-09 2012-08-15 四川大学 一种导热聚甲醛复合材料及其制备方法
CN102675818A (zh) * 2012-05-24 2012-09-19 兖矿鲁南化肥厂 一种增强增韧聚甲醛及其制备方法
JP2014122264A (ja) * 2012-12-20 2014-07-03 Asahi Kasei Chemicals Corp 導電性ポリアセタール樹脂組成物のペレット及びその製造方法
US20150318072A1 (en) * 2012-12-28 2015-11-05 Korea Engineering Plastics Co., Ltd. Carbon nanotube-polyoxymethylene resin composition having excellent electrical conductivity and improved processability and heat stability, and molded article formed therefrom
CN103897331A (zh) * 2014-04-21 2014-07-02 四川大学 一种导热聚甲醛复合材料及其制备方法
JP2015209474A (ja) * 2014-04-25 2015-11-24 ポリプラスチックス株式会社 ポリアセタール樹脂組成物、及びこのポリアセタール樹脂組成物の成形品を備える硫黄燃料接触体
JP2016020453A (ja) * 2014-07-15 2016-02-04 阪本薬品工業株式会社 ポリグリセリン系樹脂可塑剤、及びそれを含有するセラミックスラリー組成物、並びにセラミック成形体
JP2018172456A (ja) * 2017-03-31 2018-11-08 ポリプラスチックス株式会社 ポリアセタール樹脂組成物
JP2019218442A (ja) * 2018-06-19 2019-12-26 ポリプラスチックス株式会社 ポリアセタール樹脂組成物
WO2022004236A1 (fr) * 2020-06-30 2022-01-06 ポリプラスチックス株式会社 Composition de résine thermoplastique, élément associé ainsi que procédé de fabrication de celui-ci, et procédé de développement de conductivité pour composition de résine thermoplastique
WO2022004235A1 (fr) * 2020-06-30 2022-01-06 ポリプラスチックス株式会社 Composition de résine thermoplastique, élément associé ainsi que procédé de fabrication de celui-ci, et procédé de développement de conductivité pour composition de résine thermoplastique
WO2022009616A1 (fr) * 2020-07-10 2022-01-13 ポリプラスチックス株式会社 Composition de résine thermoplastique, élément, et procédé de fabrication et procédé d'amélioration de résistance mécanique pour élément formé à partir d'une composition de résine thermoplastique

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2022075107A1 (fr) * 2020-10-09 2022-04-14
JP7217384B2 (ja) 2020-10-09 2023-02-02 ポリプラスチックス株式会社 ポリアセタール樹脂組成物及び自動車部品

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