WO2014065376A1 - Élément résistant à l'effet corona, composition de résine résistant à l'effet corona et procédé de mise au point d'une résistance à l'effet corona d'un objet moulé en résine - Google Patents

Élément résistant à l'effet corona, composition de résine résistant à l'effet corona et procédé de mise au point d'une résistance à l'effet corona d'un objet moulé en résine Download PDF

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WO2014065376A1
WO2014065376A1 PCT/JP2013/078851 JP2013078851W WO2014065376A1 WO 2014065376 A1 WO2014065376 A1 WO 2014065376A1 JP 2013078851 W JP2013078851 W JP 2013078851W WO 2014065376 A1 WO2014065376 A1 WO 2014065376A1
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inorganic filler
corona
plate
resin
resistant member
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PCT/JP2013/078851
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English (en)
Japanese (ja)
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博樹 荒井
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ポリプラスチックス株式会社
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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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
    • 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
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • 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
    • C08K3/40—Glass
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/16—Solid spheres
    • C08K7/18—Solid spheres inorganic
    • C08K7/20—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
    • C08J2381/04—Polysulfides
    • 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
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate

Definitions

  • the present invention relates to a corona-resistant member having durability against corona discharge, a corona-resistant resin composition used for molding the corona-resistant member, and a method for expressing the corona resistance of a resin molded product.
  • PAS resins polyarylene sulfide resins having the required performance
  • the corona resistance alone is insufficient with the PAS resin alone, and various proposals for imparting the corona resistance to the resin molded product (composition) have been made (see, for example, Patent Documents 1 to 3).
  • Patent Document 1 a material (biaxially stretched film) made of polyphenylene sulfide (hereinafter also referred to as “PPS resin”) whose corona resistance is improved by setting the sodium chloride content to 0.5% by weight or less. ) Is disclosed. Further, Patent Documents 2 and 3 describe molded products (cable parts, hard-to-snow rings) made of a resin composition containing a PAS resin, conductive carbon black, graphite, and an epoxy group-containing ⁇ -olefin copolymer. ) Is disclosed. This is the pursuit of various performances such as heat resistance, weather resistance, flame resistance, waterproofness, airtightness, and toughness as well as corona resistance, etc. by setting the volume resistivity of the resin composition to an appropriate value. is there.
  • PPS resin polyphenylene sulfide
  • JP 59-79903 A JP-A-11-53943 JP-A-11-150848
  • the resin compositions (molded articles) described in the above-mentioned patent documents 1 to 3 provide a corona resistance effect of a certain level or more, but are not sufficient and leave room for improvement.
  • the resin component (molded product) described in the above patent document is a PAS resin (PPS resin), but corona resistance is required regardless of the type of resin in an environment exposed to corona discharge. Is done.
  • the present invention has been made in view of the above-mentioned conventional problems, and the problem is that a corona-resistant member having sufficient durability against corona discharge, a corona-resistant resin composition used for molding the corona-resistant member, And it is providing the corona-resistance expression method of a resin molded product.
  • the plate-like inorganic filler after molding has a mode diameter of 1 to 200 ⁇ m in a volume-based particle size distribution measured by a laser diffraction / scattering method
  • the mode diameter in the volume-based particle size distribution measured by a laser diffraction / scattering method of the granular inorganic filler after molding is 0.1 to 50 ⁇ m
  • the inorganic filler is a fibrous inorganic filler
  • (10) A method of developing corona resistance of a resin molded product obtained by molding the resin composition by adding a plate-like, granular or fibrous inorganic filler to the resin composition,
  • the plate-like inorganic filler after molding so that the mode diameter in the volume-based particle size distribution measured by a laser diffraction / scattering method is 1 to 200 ⁇ m.
  • the inorganic filler is a granular inorganic filler
  • the granular inorganic filler is molded so that the mode diameter in the volume-based particle size distribution measured by a laser diffraction / scattering method is 0.1 to 50 ⁇ m.
  • the inorganic filler is a fibrous inorganic filler
  • the corona resistance of the resin molded product to which the fibrous inorganic filler is added so that the fiber diameter of the fibrous inorganic filler in the corona resistant resin composition is 3 to 9 ⁇ m. Expression method.
  • a corona-resistant member having sufficient durability against corona discharge a corona-resistant resin composition used for molding the corona-resistant member, and a method for expressing corona resistance of a resin molded product are provided. Can do.
  • the corona-resistant member of the present invention is a corona-resistant member formed by molding a corona-resistant resin composition obtained by melt-kneading at least a resin component and a plate-like, granular or fibrous inorganic filler.
  • the inorganic filler is a plate-like inorganic filler
  • the plate-like inorganic filler after molding has a mode diameter in a volume-based particle size distribution measured by a laser diffraction / scattering method of 1 to 200 ⁇ m
  • the inorganic filler is In the case of a granular inorganic filler, when the granular inorganic filler after molding has a mode diameter in a volume-based particle size distribution measured by a laser diffraction / scattering method of 0.1 to 50 ⁇ m, and the inorganic filler is a fibrous inorganic filler
  • the fiber diameter of the fibrous inorganic filler in the corona-resistant resin composition is 3 to 9 ⁇ m.
  • the corona-resistant member of the present invention is formed by molding a corona-resistant resin composition containing an inorganic filler having a predetermined shape, and an electric tree generated when the corona-resistant member is exposed to corona discharge.
  • the above-mentioned inorganic filler efficiently hinders and delays the progress of dendritic local destruction called. Specifically, for the plate-like inorganic filler, the plate-like shape delays the progress of the electric tree, and for the granular inorganic filler and the fibrous inorganic filler, the specific surface area is large, respectively.
  • the corona-resistant resin composition used for molding the corona-resistant member of the present invention will be described below.
  • the corona-resistant resin composition of the present invention is used for molding the corona-resistant member of the present invention, and is obtained by melt-kneading a resin component and a predetermined plate-like, granular or fibrous inorganic filler. can get. Below, each component of the corona-resistant resin composition of this invention is explained in full detail.
  • the resin component is not particularly limited.
  • the resin component is not particularly limited.
  • Two or more kinds of resin components may be used in combination.
  • polyarylene sulfide resin polybutylene terephthalate resin (hereinafter also referred to as “PBT resin”)
  • PBT resin polybutylene terephthalate resin
  • polyacetal resin polyacetal resin
  • liquid crystal resin etc.
  • engineering plastic Because of its excellent and workability, it is generically called engineering plastic and is used in a wide range of applications such as automobiles, electrical / electronic parts, etc.
  • PAS resin and the PBT resin will be sequentially described.
  • the PAS resin is a polymer compound mainly composed of — (Ar—S) — (wherein Ar is an arylene group) as a repeating unit, and a PAS resin having a molecular structure generally known in the present invention is used. can do.
  • arylene group examples include p-phenylene group, m-phenylene group, o-phenylene group, substituted phenylene group, p, p′-diphenylene sulfone group, p, p′-biphenylene group, p, p′-.
  • examples thereof include a diphenylene ether group, p, p′-diphenylenecarbonyl group, and naphthalene group.
  • the PAS resin may be a homopolymer consisting only of the above repeating units, or a copolymer containing the following different types of repeating units may be preferable from the viewpoint of processability and the like.
  • a polyphenylene sulfide resin (hereinafter also referred to as “PPS resin”) in which p-phenylene group is used as an arylene group and p-phenylene sulfide group is a repeating unit is preferably used.
  • PPS resin polyphenylene sulfide resin
  • the copolymer among the arylene sulfide groups comprising the above-mentioned arylene groups, two or more different combinations can be used, and among them, a combination containing a p-phenylene sulfide group and an m-phenylene sulfide group is particularly preferably used. It is done.
  • those containing p-phenylene sulfide groups of 70 mol% or more, preferably 80 mol% or more are suitable from the viewpoint of physical properties such as heat resistance, moldability and mechanical properties.
  • a high molecular weight polymer having a substantially linear structure obtained by condensation polymerization from a monomer mainly composed of a bifunctional halogen aromatic compound can be particularly preferably used. Two or more different types of molecular weight PAS resins may be mixed and used.
  • a partially branched or crosslinked structure is formed by using a small amount of a monomer such as a polyhaloaromatic compound having 3 or more halogen substituents when performing condensation polymerization.
  • a monomer such as a polyhaloaromatic compound having 3 or more halogen substituents
  • examples thereof include polymers obtained by heating a polymer having a low molecular weight and a linear structure polymer having a low molecular weight at a high temperature in the presence of oxygen or the like to increase the melt viscosity by oxidative crosslinking or thermal crosslinking, thereby improving molding processability.
  • the melt viscosity (310 ° C., shear rate 1216 sec ⁇ 1 ) of the PAS resin as the base resin used in the present invention is preferably 600 Pa ⁇ s or less, including the above mixed system, and is in the range of 8 to 300 Pa ⁇ s. Those having a good balance between mechanical properties and fluidity are particularly preferred.
  • the PBT resin includes a dicarboxylic acid component containing at least terephthalic acid or an ester-forming derivative thereof (such as a lower alcohol ester), an alkylene glycol (1,4-butanediol) having at least 4 carbon atoms or an ester-forming derivative thereof (acetyl).
  • the PBT resin is not limited to a homo PBT resin, but may be a copolymer (copolymerized PBT resin) containing 60 mol% or more (particularly 75 mol% or more and 95 mol% or less) of a butylene terephthalate unit.
  • dicarboxylic acid components other than terephthalic acid and its ester-forming derivatives
  • aromatic dicarboxylic acid components isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, diphenyl ether dicarboxylic acid, etc., C 6 -C 12 aryl dicarboxylic acid etc.
  • aliphatic dicarboxylic acid component C 4 -C 16 alkyl dicarboxylic acid such as succinic acid, adipic acid, azelaic acid, sebacic acid, etc.
  • C 5 -C 10 cyclo such as cyclohexane dicarboxylic acid, etc.
  • Alkyl dicarboxylic acids and the like or ester-forming derivatives of these dicarboxylic acid components.
  • These dicarboxylic acid components can be used alone or in combination of two or more.
  • Preferred dicarboxylic acid components include aromatic dicarboxylic acid components (especially C 6 -C 10 aryl dicarboxylic acids such as isophthalic acid) and aliphatic dicarboxylic acid components (particularly C such as adipic acid, azelaic acid and sebacic acid). 6 ⁇ C 12 alkyl dicarboxylic acids) are included.
  • an aliphatic diol component for example, alkylene glycol (ethylene glycol, propylene glycol, trimethylene glycol, 1,3-butylene glycol, hexamethylene glycol, neopentyl glycol, C 2 ⁇ C 10 alkylene glycols such as 1,3-octanediol, diethylene glycol, triethylene glycol, polyoxy C 2 ⁇ C 4 alkylene glycol such as dipropylene glycol), cyclohexane dimethanol, Alicyclic diols such as hydrogenated bisphenol A], aromatic diol components [aromatic alcohols such as bisphenol A 4,4-dihydroxybiphenyl, bisphenol A 2 ⁇ C 4 alkylene oxide adduct (e.g., ethylene oxide 2 mol adduct of bisphenol A, propylene oxide 3 mol ad
  • Preferred glycol components include aliphatic diol components (especially polyoxy C 2 -C 3 alkylene glycols such as C 2 -C 6 alkylene glycol, diethylene glycol, and cycloaliphatic diols such as cyclohexane dimethanol). .
  • any of the homo PBT resin or copolymer PBT resin produced by polycondensation using the above compound as a monomer component can be used as the resin component of the present invention.
  • the homo PBT resin and copolymer PBT resin can be used alone or in admixture of two or more.
  • the plate-like shape in the plate-like inorganic filler means a shape having a different diameter ratio larger than 4 (aspect ratio is 1 to 1500), and the particle shape in the granular inorganic filler is 1 to 4 in different diameter ratio.
  • it refers to a shape (including spherical shape) having an aspect ratio of 1 to 2
  • the fibrous shape in the fibrous inorganic filler is a shape having a different diameter ratio of 1 to 4 and an aspect ratio of 2 to 1500.
  • any shape is an initial shape (shape before melt-kneading).
  • the different diameter ratio is “the major axis of the cross section perpendicular to the longitudinal direction (the longest linear distance of the cross section) / the minor axis (the longest linear distance of the major axis to the right direction)”
  • the aspect ratio is “ The longest linear distance in the longitudinal direction / the short diameter of the cross section perpendicular to the longitudinal direction (the “longest linear distance in the cross section” and the longest linear distance in the perpendicular direction) ”.
  • Plate-like inorganic filler those having a mode diameter of 1 to 200 ⁇ m in the volume-based particle size distribution measured by the laser diffraction / scattering method of the plate-like inorganic filler after molding are used.
  • the thickness of the plate-like inorganic filler the thinner the thickness (for example, the average thickness is 20 ⁇ m or less), the more the absolute number of the sheets increases, so that the specific surface area increases and the labyrinth effect increases.
  • the plate-like inorganic filler is not particularly limited as long as it can delay the progress of the electric tree.
  • glass that is, glass flake
  • talc plate
  • mica Kaolin
  • clay clay
  • alumina alumina
  • glass and talc are preferably used.
  • glass flakes (marketed products) usable in the present invention for example, REFG-108 (average particle diameter (50% d): 623 ⁇ m) manufactured by Nippon Sheet Glass Co., Ltd., Fine Flakes (manufactured by Nippon Sheet Glass Co., Ltd.) Average particle diameter (50% d): 169 ⁇ m), manufactured by Nippon Sheet Glass Co., Ltd., REFG-301 (average particle diameter (50% d): 155 ⁇ m), manufactured by Nippon Sheet Glass Co., Ltd., REFG-401 (average particle diameter ( 50% d): 310 ⁇ m) and the like.
  • REFG-108 average particle diameter (50% d): 623 ⁇ m
  • Fine Flakes manufactured by Nippon Sheet Glass Co., Ltd.
  • REFG-301 average particle diameter (50% d): 155 ⁇ m
  • REFG-401 average particle diameter ( 50% d): 310 ⁇ m) and the like.
  • examples of talc (commercially available product) that can be used in the present invention include Crown Talc PP manufactured by Matsumura Sangyo Co., Ltd., and Talcan Powder PKNN manufactured by Hayashi Kasei Co., Ltd.
  • examples of mica (marketed product) that can be used in the present invention gold mica includes 150-S (average particle size (50% d): 163 ⁇ m), 325-S (average particle size) manufactured by West Japan Trading Co., Ltd. Diameter (50% d): 30 ⁇ m), 60-S (average particle diameter (50% d): 278 ⁇ m), etc.
  • the average particle diameter (50% d) means a median diameter of 50% integrated value in the particle size distribution measured by the laser diffraction / scattering method.
  • the granular inorganic filler As the granular inorganic filler, those having a mode diameter of 0.1 to 50 ⁇ m in the volume-based particle size distribution measured by a laser diffraction / scattering method of the granular inorganic filler after molding are used.
  • the particulate inorganic filler is not particularly limited as long as it has a large specific surface area and can delay the progress of the electric tree.
  • glass that is, glass beads
  • calcium carbonate that is, glass beads
  • talc talc
  • silica those made of glass, calcium carbonate and silica are preferably used.
  • a spherical inorganic filler is particularly preferable because it is speculated that discharge is mitigated by surface smoothness.
  • glass beads that can be used in the present invention those that are commercially available include Potters Barotini, GL-BS (average particle size (50% d): 21 ⁇ m), Potters Barotini, And EMB-10 (average particle size (50% d): 5 ⁇ m).
  • Examples of calcium carbonate include Toray Fine Chemical Co., Ltd., Whiten P-30 (average particle size (50% d): 5 ⁇ m), and the like.
  • Examples of the silica include SC2000-ZD (average particle size (50% d): 0.5 ⁇ m) manufactured by Admatechs Co., Ltd.
  • Fibrous inorganic filler those having a fiber diameter of 3 to 9 ⁇ m are used. When the fiber diameter exceeds 9 ⁇ m, the specific surface area cannot be increased and the corona resistance effect tends not to be sufficiently exhibited, and those having a fiber diameter of less than 3 ⁇ m are difficult to manufacture and difficult to obtain.
  • the fiber diameter is preferably 3 to 6 ⁇ m.
  • the fibrous inorganic filler is not limited as long as the specific surface area is large, and examples thereof include glass (that is, glass fiber), whisker, and wollastonite. Those made of glass are preferably used.
  • Examples of commercially available glass fibers that can be used in the present invention include those manufactured by Nippon Electric Glass Co., Ltd., chopped glass fibers (ECS03T-790DE, average fiber diameter: 6 ⁇ m), manufactured by Fuji Fiber Glass Co., Ltd. And chopped glass fibers (CS 3DE-257, average fiber diameter: 6 ⁇ m), manufactured by Owens Corning Manufacturing Co., Ltd., chopped glass fibers (CS03DE 416A, average fiber diameter: 6 ⁇ m), and the like.
  • the content is preferably 25 to 101 parts by mass, and 40 to 70 parts by mass with respect to 100 parts by mass of the PAS resin, from the viewpoint of obtaining sufficient corona resistance. It is more preferable.
  • the corona-resistant resin composition according to the present invention is a lubricant, carbon black, a nucleating agent, a flame retardant, a flame retardant aid, an antioxidant, a metal deactivator, and other anti-aging agents as long as the effects of the present invention are not impaired. It may contain an additive, a polymer such as a UV absorber, a stabilizer, a plasticizer, a pigment, a dye, a colorant, an antistatic agent, a foaming agent, other resins, and additives.
  • a polymer such as a UV absorber, a stabilizer, a plasticizer, a pigment, a dye, a colorant, an antistatic agent, a foaming agent, other resins, and additives.
  • the method for expressing the corona resistance of the resin molded product of the present invention is a method of corona resistance of a resin molded product obtained by molding the resin composition by adding a plate-like, granular or fibrous inorganic filler to the resin composition.
  • the inorganic filler is a plate-like inorganic filler
  • the plate-like inorganic filler after molding has a mode diameter of 1 to 200 ⁇ m in a volume-based particle size distribution measured by a laser diffraction / scattering method.
  • the mode diameter in the volume-based particle size distribution measured by the laser diffraction / scattering method of the granular inorganic filler after molding is 0.
  • the particulate inorganic filler is added so as to have a thickness of 1 to 50 ⁇ m, and the inorganic filler is a fibrous inorganic filler
  • the fiber in the corona-resistant resin composition The fibrous inorganic filler is added so that the fiber diameter of the fibrous inorganic filler is 3 to 9 ⁇ m.
  • the corona-resistant member of the present invention exhibits corona resistance by adding a predetermined inorganic filler.
  • Sex can be expressed.
  • the resin component and the inorganic filler in the method for expressing the corona resistance of the resin molded product of the present invention are the same as the resin component and the inorganic filler in the corona resistant resin composition of the present invention described above, in order to develop the corona resistance. The same applies to preferred examples, addition amounts, and other components that can be added.
  • the corona-resistant member of the present invention is formed by molding the corona-resistant resin composition of the present invention described above, but there is no particular limitation on the production method, and a known method can be adopted.
  • the corona-resistant resin composition of the present invention which will be described later, is put into an extruder, melted and kneaded into pellets, and the pellets are put into an injection molding machine equipped with a predetermined mold and produced by injection molding. can do.
  • the mode diameter in the volume-based particle size distribution measured by the laser diffraction / scattering method of the plate-like inorganic filler in the corona-resistant member is 1 to 200 ⁇ m. It is preferably 15 to 150 ⁇ m, more preferably 40 to 130 ⁇ m. If the mode diameter of the plate-like inorganic filler in the corona-resistant member is less than 1 ⁇ m (or the length is too short), it will be swallowed by the fountain flow and will be perpendicular to the flow direction. The effect tends to decrease.
  • the mode diameter of the plate-like inorganic filler in the corona-resistant member can be measured using a laser diffraction / scattering particle size distribution analyzer LA-920 manufactured by Horiba, Ltd.
  • the mode diameter in the volume-based particle size distribution measured by the laser diffraction / scattering method of the granular inorganic filler in the corona-resistant member is 0.1 to 50 ⁇ m. It is preferably 0.1 to 25 ⁇ m, more preferably 0.1 to 10 ⁇ m.
  • the mode diameter of the granular inorganic filler in the corona-resistant member is less than 0.1 ⁇ m, the corona-resistant effect tends to be reduced.
  • the mode diameter of the particulate inorganic filler in the corona-resistant member can be measured using a laser diffraction / scattering particle size distribution measuring apparatus LA-920 manufactured by Horiba, Ltd.
  • the plate-like inorganic filler is preferably oriented so as to be orthogonal to the voltage direction caused by corona discharge. Specifically, when a voltage is applied to the corona-resistant member, the plate-like inorganic filler is oriented to be orthogonal to the voltage application direction, in other words, to be orthogonal to the voltage direction due to corona discharge.
  • the plate-like inorganic filler in the corona-resistant member is preferably oriented in one direction so as to be parallel to each other.
  • the orientation direction of the plate-like inorganic filler is orthogonal to the voltage direction caused by the corona discharge means that the normal direction of the plate-like inorganic filler and the voltage direction caused by the corona discharge coincide with each other, The normal direction and the voltage direction do not have to be completely coincident with each other, and may be deviated as long as the effects of the present invention are not impaired.
  • the orientation state of the said plate-shaped inorganic filler is demonstrated with reference to FIG.2 and FIG.3.
  • FIG. 2 and 3 schematically show how a high voltage is applied to the corona-resistant member.
  • the high voltage electrode 12 is disposed above the flat corona-resistant members 10A and 10B, and the ground side electrode 14 is disposed below the high voltage electrode when high frequency / high voltage is applied by both electrodes.
  • Corona discharge is generated in the vicinity of the tip of 12, and the surfaces of the corona-resistant members 10A and 10B are exposed to corona discharge.
  • the plate-like inorganic filler 16 is oriented in the corona-resistant member 10A so as to be orthogonal to the voltage application direction.
  • the plate-like inorganic filler 16 is oriented so as to be parallel to the voltage direction.
  • the plate-like inorganic filler 16 when corona discharge is generated by applying a high frequency / high voltage, the plate-like inorganic filler 16 is oriented so as to obstruct the progress of the electrical tree in the configuration of FIG. Therefore, the progress can be delayed. As a result, it is thought that the lifetime improvement of 10 A of corona-resistant members can be achieved.
  • the configuration of FIG. 3 there are many gaps in the traveling direction of the electric tree, and the obstruction effect of the electric tree is small.
  • the corona-resistant member having the plate-like inorganic filler oriented as shown in FIG. 2 is arranged so that the plate-like inorganic filler inside thereof is orthogonal to the voltage application direction caused by corona discharge. The effect of corona property can be exhibited more effectively.
  • the desired direction for orienting the plate-like inorganic filler is the flow direction of the resin. This can be realized by setting the gate position of the mold.
  • the shape of the corona-resistant member can be, for example, a sheet shape, a plate shape, a cylindrical shape, or a film shape.
  • the corona discharge generated due to the voltage applied in the thickness direction of the member is excellent.
  • Durability can be expressed.
  • a sheet-like corona-resistant member when a high frequency / high voltage is applied in the thickness direction of the sheet, that is, in a direction perpendicular to the sheet surface, the electrical tree advances in the sheet thickness direction by corona discharge.
  • the plate-like inorganic filler is oriented as described above, the progress of the electric tree can be most effectively prevented, and the life of the sheet-like corona-resistant member can be extended. The same applies to other shapes.
  • the corona-resistant member of the present invention can be used as a member that requires corona resistance.
  • Examples of such a member include a casing of an ignition coil, an insulated wire, and an electrical insulating sheet.
  • Examples 1 to 9, Comparative Examples 1 to 9 In each example and comparative example, the mixture obtained by dry blending each raw material component shown in Table 1 and Table 2 was put into a twin screw extruder having a cylinder temperature of 320 ° C. (glass fiber, glass fiber with different diameter cross section, Milled fiber, glass beads, glass flakes and mica were added separately from the side feed part of the extruder), melt-kneaded and pelletized. The detail of each raw material component shown in Table 1 and Table 2 is described below.
  • PAS resin component PPS resin manufactured by Kureha Co., Ltd., Fortron KPS W214A (melt viscosity: 130 Pa ⁇ s (shear rate: 1216 sec ⁇ 1 , 310 ° C.))
  • the melt viscosity of the PPS resin was measured as follows. (Measurement of melt viscosity of PPS resin) Using a Capillograph manufactured by Toyo Seiki Co., Ltd., a melt viscosity at a barrel temperature of 310 ° C. and a shear rate of 1216 sec ⁇ 1 was measured using a 1 mm ⁇ ⁇ 20 mmL / flat die as a capillary.
  • Fibrous inorganic filler Glass fiber 1 Chopped glass fiber (manufactured by Nippon Electric Glass Co., Ltd., ECS03T-790DE), average fiber diameter: 6 ⁇ m
  • Glass fiber 2 Chopped glass fiber (manufactured by Nippon Electric Glass Co., Ltd., ECS03T747), average fiber diameter: 13 ⁇ m
  • Different diameter cross section glass 1 Flat glass (manufactured by Nitto Boseki Co., Ltd., CSG3PL830S), different diameter ratio 2 (10 ⁇ m ⁇ 20 ⁇ m)
  • Different diameter cross section glass 2 flat glass (manufactured by Nitto Boseki Co., Ltd., CSG3PA830S), different diameter ratio 4 (7 ⁇ m ⁇ 28 ⁇ m)
  • Milled fiber 1 manufactured by Nitto Boseki Co., Ltd., PF70E-001, average fiber diameter: 10 ⁇ m
  • the average particle size (50% d) of the inorganic filler was measured as follows. (Measurement of average particle size (50% d) of inorganic filler) Using a laser diffraction / scattering particle size distribution analyzer LA-920 manufactured by HORIBA, Ltd. Under the following measurement conditions, the particle size distribution of each inorganic filler and the integrated value in the particle size distribution measured by the laser diffraction / scattering method A median diameter of 50% was measured.
  • test piece 10 produced in each of the examples and comparative examples was fixed between a high voltage side electrode 12 ( ⁇ 9.5 mm) and a ground side electrode 14 ( ⁇ 25 mm), and a withstand voltage tester (Yamayo) Using a test machine YST-243WS-28), a temperature of 130 ° C., a frequency of 200 Hz and an applied voltage of 18 kV was applied in air, and the time until dielectric breakdown occurred was measured. The measurement results are shown in Tables 1 and 2.
  • Examples 1 to 9 all had a long-term durability of 50 hours or more in the corona resistance test, whereas in Comparative Examples 1 to 9, the test was less than 50 hours. It can be seen that satisfactory results were not obtained. Moreover, regarding the glass beads, it can be seen that the corona resistance is improved as the mode diameter is reduced. In addition, among the granular inorganic fillers, a comparison between Examples 5, 6, and 9 using the spherical inorganic filler and Example 8 using the non-spherical granular inorganic filler shows that the spherical inorganic filler is particularly spherical inorganic. It can be seen that the corona resistance is improved by the filler.

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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
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Abstract

L'invention concerne un élément résistant à l'effet corona, présentant une résistance suffisamment longue à une décharge par effet corona et une composition de résine résistant à l'effet corona utilisée dans le moulage dudit élément résistant à l'effet corona. Cet élément résistant à l'effet corona est formé par moulage d'une composition de résine résistant à l'effet corona obtenue par fusion et mélange d'au moins un constituant de type résine et d'une charge en plaques, granulaire ou fibreuse ; cette composition de résine résistant à l'effet corona est utilisée dans le moulage d'éléments résistant à l'effet corona. Dans le cas d'une charge inorganique en plaques, le diamètre modal dans la distribution des particules sur base du volume, mesurée par un procédé de diffraction/diffusion de rayon laser après le moulage, est de préférence de 1-200 μm ; dans le cas d'une charge inorganique granulaire, le diamètre modal susmentionné est de préférence de 0,1-50 μm ; et dans le cas d'une charge inorganique fibreuse, le diamètre des fibres dans la composition de résine est de préférence de 3-9 μm.
PCT/JP2013/078851 2012-10-26 2013-10-24 Élément résistant à l'effet corona, composition de résine résistant à l'effet corona et procédé de mise au point d'une résistance à l'effet corona d'un objet moulé en résine WO2014065376A1 (fr)

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WO2015064499A1 (fr) * 2013-10-29 2015-05-07 ポリプラスチックス株式会社 Composition de résine résistant à l'effet corona, procédé de mise au point de résistance à l'effet corona d'une composition de résine, et élément résistant à l'effet corona
WO2017057558A1 (fr) * 2015-10-02 2017-04-06 Dic株式会社 Composition de résine de poly(sulfure d'arylène), article moulé, et procédé de production
JP2019014880A (ja) * 2017-07-05 2019-01-31 ポリプラスチックス株式会社 ガスバリア性部材用樹脂組成物

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WO2017057558A1 (fr) * 2015-10-02 2017-04-06 Dic株式会社 Composition de résine de poly(sulfure d'arylène), article moulé, et procédé de production
JPWO2017057558A1 (ja) * 2015-10-02 2018-07-05 Dic株式会社 ポリアリーレンスルフィド樹脂組成物、成形品及び製造方法
JP2019014880A (ja) * 2017-07-05 2019-01-31 ポリプラスチックス株式会社 ガスバリア性部材用樹脂組成物
JP7126879B2 (ja) 2017-07-05 2022-08-29 ポリプラスチックス株式会社 ガスバリア性部材用樹脂組成物

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